Abstract Book - International Symposium on Molecular Spectroscopy

Transcription

Welcome to the 68th
OSU International
Symposium on Molecular Spectroscopy
On behalf of the Executive Committee, Frank DeLucia, Anne B. McCoy, and myself, I extend a heartfelt welcome to all the attendees to the 68th Symposium and
welcome you to The Ohio State University and Columbus. The Symposium presents
research in fundamental molecular spectroscopy and a wide variety of related fields
and applications. The continued vitality and significance of spectroscopy is annually
re-affirmed by the number of talks, their variety, and the fact that many are given by
students. These presentations are the heart of the meeting and are documented by this
Abstract Book. Equally important is the information flowing from informal exchanges
and discussions. As organizers, we strive to provide an environment that facilitates
both kinds of interactions.
This 68th Symposium marks the end of an uninterrupted series of annual meetings
at The Ohio State University extending more than two-third’s of a Century. The fact
that the number of talks scheduled at this year’s meeting far exceeds that of any of
the prior 67 is certainly auspicious for the future of the Symposium. Next year the
meeting will move to the University of Illinois, where I anticipate it will continue to
thrive under the leadership of Ben McCall and his colleagues. It has been my honor
and pleasure to serve as Symposium Chair for 22 meetings. I want to express my
sincere gratitude to the members, past and present, of the Executive and International
Advisory Committees for all their help. Most of all I salute the attendees who have
made the Symposium such a success. I expect to attend and enjoy next year’s meeting
at the University of Illinois and I hope that all of you share my expectation.
Terry A. Miller
Symposium Chair
Contents
SCHEDULE OF TALKS
ABSTRACTS
Monday (M)....................1
Monday (M)..................106
Tuesday (T)...................20
Tuesday (T)...................150
Wednesday (W).............48
Wednesday (W).............218
Thursday (R)..................67
Thursday (R).................265
Friday (F).......................95
Friday (F)......................333
AUTHOR INDEX...................360
ACKNOWLEDGMENTS.......369
68th OSU INTERNATIONAL SYMPOSIUM
ON MOLECULAR SPECTROSCOPY
JUNE 17-21, 2013
International Advisory Committee
Jose Dominech, CSIC
Geoffrey Duxbury, U Strathclyde Glasgow
Thomas Giesen, U. Cologne
Michael Heaven, Emory U.*, Chair
Caroline Jarrold, Indiana U. Bloomington*
Mark Johnson, Yale University
Hideto Kanamori, Tokyo Inst. of Tech.
*steering committee member
e-mail: [email protected]
Executive Committee
Terry A. Miller, Chair
Frank C. DeLucia
Anne B. McCoy
Please send correspondence to:
Terry A. Miller
International Symposium on
Molecular Spectroscopy
Department of Chemistry
100 West 18th Avenue
Columbus, Ohio 43210 USA
http://molspect.chemistry.ohio-state.edu/symposium/
International Advisory Committee
Isabelle Kleiner, CNRS
Sang Kuk Lee, Pusan National U.
Nasser Moazzen-Ahmadi, U. Calgary
Leah O’Brien, S. Illinois U. Edwardsville*
Trevor Sears, Brookhaven National Lab
Ned Sibert, U. Wisconsin
David Dale Skatrud, ARO
Mary Ann Smith, NASA, Langley Research
John Stanton, U. Texas*
*steering committee member
614-292-2569 (phone),-1948 (FAX)
Special Sessions
For the 68th Symposium, Wim Ubachs, Vrije Universiteit Amsterdam, and Tim Steimle, Arizona State University, are
organizing a mini-symposium entitled, “Spectroscopy Tests of Fundamental Physics”. This mini-symposium will focus
on experimental and theoretical efforts to characterize shifts in molecular quantum levels brought about by physics beyond the principles of General Relativity and the Standard Model. Invited speakers include Peter Schwerdtfeger, Massey
University, and Wim Ubachs, Vrije Universiteit Amsterdam. A second mini-symposium is being organized by Vincent
Boudon, CNRS/Universite de Bourgogne and Peter Bernath, Old Dominion University on the subject of “Spectroscopy
of Planetary Atmospheres.” This mini-symposium is dedicated to the spectroscopy of planetary atmospheres including
observations, laboratory measurements and modeling for the Earth, planets of the Solar System, exoplanets and brown
dwarfs. Invited talks for this mini-symposium will be given by Pierre-Francois Coheur, Universite Libre de Bruxelles;
and Glenn Orton, JPL-California Institute of Technology; and Jonathan Tennyson, University College London. A third
mini-symposium is being organized by John Stanton, University of Texas at Austin entitled “Theory and Spectroscopy.”
This symposium will focus on the development, and use of, theoretical tools for addressing spectroscopic problems. Invited speakers include Jon Hougen, NIST, Horst Koeppel, Universitaet Heidelberg; Timothy Lee, NASA; and Cristina
Puzzarini, Universita di Bologna.
Picnic
The Symposium picnic will be held on Wednesday evening, June 19, at the Fawcett Center. The cost of the picnic is
included in your registration (at below cost to students), so that all may attend the event. The Coblentz Society is the host
for refreshments at 6:30pm before the picnic which is scheduled to commence at 7:30pm at the Fawcett Center.
Sponsorship
We are pleased to announce the sponsorship for the 68th Symposium. Principal funding comes from the Army Office of
Research (ARO). We are most grateful to ARO for their continued support. We also acknowledge the many efforts and
contributions of The Ohio State University in hosting the meeting. Our Corporate sponsors are Elsevier, Coherent the
Journal of Physical Chemistry A and Quantel. Please see the back of this book for their advertisements and the events
they support. We are pleased to acknowledge Altos Photonics, Block Engineering, Bristol Instruments, Bruker Optics, Clark-MXR, Continuum, CVI Laser Optics, Lockheed Martin/Aculight, MSquared Lasers, Newport/SpectraPhysics, Princeton Instruments, and Toptica Photonics as Contributing sponsors. IOS Press has a special insert in your
conferee packet. Bruker Optics will have a special Tuesday lunch presentation. Look in your packet for fliers about that.
Our sponsors will have exhibits at the Symposium and we encourage you to visit their displays.
Rao Prize
The three Rao Prizes for the most outstanding student talks at the 2012 meeting will be presented. The winners are
Nils Bartels, Georg August Universitaet Goettingen; Andrew Petit, The Ohio State University; and Arron Wolk, Yale
University. The Rao Prize was created by a group of spectroscopists who, as graduate students, benefited from the emphasis
on graduate student participation, which has been a unique characteristic of the Symposium. This year three more Rao
Prizes will be awarded. The award is administered by a Prize Committee chaired by Yunjie Xu, University of Alberta
and comprised of Kevin Lehmann, University of Virginia; Brooks Pate, University of Virginia; Rebecca Peebles, Eastern
Illinois University; Brenda Winnewisser, The Ohio State University and Tim Zwier, Purdue University. Any questions or
suggestions about the Prize should be addressed to the Committee. Anyone (especially post-docs) willing to serve on a
panel of judges should contact Yunjie Xu ([email protected]).
Information
ACCOMMODATIONS: The check-in for dormitory accommodations is located in the Lane Avenue Residence Hall
(LARH), 328 W. Lane Avenue, opens at 10a.m. Sunday, June 16, and remains open 24 hours a day through the Symposium.
Other hotels close to campus include: The Blackwell, corner of Tuttle Park Place and Woodruff Avenue, 866-247-4003,
and Red Roof Inn, State Route 315 & Ackerman Rd., 267-9941. NOTE: When making reservations with the Blackwell
mention that you are with the Molspec Symposium and you will be given the OSU discount, if rooms are still available.
MAIL: As in recent years, computer facilities for email will be available. Address your regular mail for delivery during
the Symposium to: c/o MOLECULAR SPECTROSCOPY SYMPOSIUM, Department of Chemistry, The Ohio State
University, 100 West 18th Avenue, Columbus, Ohio, 43210, U.S.A. FAX number - (614) 292-1948, Telephone number (614) 292-2569.
PARKING: Parking permits, for the week, are available only from the check-in desk at the Lane Avenue Residence
Hall. These permits allow you to park in any “C” parking space on campus. The permit must be displayed on the front
windshield of your car. Please follow all traffic rules to avoid the issuance of tickets. NOTE: The Symposium takes place
during Summer Session so parking on campus can be problematic.
REGISTRATION: The Registration Desk will be located in Room 2017 McPherson Lab. It will be open between
4:00-6:00 p.m. Sunday, and 8:00a.m. - 4:30p.m., Monday through Friday. Those who have prepaid their registration
and who are staying in the dorms will receive their registration packet at LARH upon check-in. If you have prepaid your
registration but are not staying at the dorms, pick up your packet at the Registration Desk. NOTE: If the dates of your
stay change after Friday, June 7, please call the Symposium Office to find out your options.
LIABILITY: The Symposium fees DO NOT include provisions for the insurance of participants against personal injuries,
sickness, theft or property damage. Participants and companions are advised to take whatever insurance they consider
necessary. Neither the Symposium organizing committee, its sponsors, nor individual committee members assume any
responsibility for loss, injury, sickness, or damages to persons or belongings, however caused. The statements and opinions
stated during oral presentations or in written abstracts are solely the author’s responsibilities and do not necessarily reflect
the opinions of the organizers.
AUDIO/VIDEO INFORMATION: Equipment for computer presentations, i.e. Powerpoint, will be available for each
session. For computer presentations, you must go to the Digital Presentation link on our web site and follow the instructions. Your PowerPoint file and all supporting documents can be uploaded. These files must be submitted to the
Symposium by MIDNIGHT THE DAY BEFORE your presentation session. All submitted files will be loaded on the
presentation computer one half-hour prior to the beginning of the session.
Please make careful note of the username (p#) and password provided in the email confirming receipt of your abstract - this
username/password combination will be required when you submit your digital presentation. If you are submitting multiple
presentations you will need to log on separately with the appropriate username and password for each presentation.
ACKNOWLEDGEMENTS: The Symposium Chair wishes to acknowledge the hard work of numerous people who make
this meeting possible. Key among these people are Becky Gregory, who solves everyone’s problems and keeps the meeting
running smoothly; and my student assistants, Terrance Codd and Brennan Walder who ensure the sessions go well. We
wish to acknowledge the hospitality of the Chemistry Department in tolerating our invasion this year. Sergey Panov
originally wrote the script for the electronic aspects of the Symposium; Computer Support in Chemistry and Physics helps
us modernize it as well as keep it and other aspects of our services operational. Finally, all the students in my group play
vital roles in helping to make sure nothing falls through the cracks.
MA. PLENARY
MONDAY, JUNE 17, 2013 – 8:45 AM
Room: AUDITORIUM, INDEPENDENCE HALL
Chair: FRANK C. DE LUCIA, The Ohio State University, Columbus, OH
Welcome
Caroline C. Whitacre, Vice President for Research
The Ohio State University
MA01
LOW TEMPERATURE TRAPPING: FROM REACTIONS TO SPECTROSCOPY
8:45
40 min 9:00
S. SCHLEMMER, O. ASVANY, and S. BRÜNKEN, I. Physikalisches Institut, Universität zu Köln,
50937 Köln, Germany.
MA02
DECODING THE EFFECTS OF LARGE AMPLITUDE VIBRATIONAL MOTIONS IN SPECTRA
40 min 9:45
ANNE B. McCOY, LAURA C. DZUGAN, MENG HUANG, ZHOU LIN, BERNICE OPOKU-AGYEMAN,
ANDREW S. PETIT, JASON FORD, and BETHANY A. WELLEN, Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH 43210.
Intermission
RAO AWARDS
Presentation of Awards by Yunjie Xu, University of Alberta
10:50
2012 Rao Award Winners
Nils Bartels, Georg August Universitaet Goettingen
Andrew Petit, The Ohio State University
Arron Wolk, Yale University
COBLENTZ AWARD
Presentation of Award by Michael L. Myrick, President, Coblentz Society
5 min
11:05
MA03
40 min
11:10
Coblentz Society Award Lecture
LINEAR AND NONLINEAR MOLECULAR SPECTROSCOPY WITH LASER FREQUENCY COMBS
NATHALIE PICQUÉ, Max Planck Institut für Quantenoptik, Hans-Kopfermann-Str. 1, 85748 Garching, Germany; Ludwig-Maximilians-Universität München, Fakultät für Physik, Schellingstrasse 4/III, 80799 München,
Germany; Institut des Sciences Moléculaires d’Orsay, Université Paris-Sud, 91405 Orsay, France; email:
[email protected].
2
MF. MINI-SYMPOSIUM: SPECTROSCOPY TESTS OF FUNDAMENTAL
PHYSICS
MONDAY, JUNE 17, 2013 – 1:30 PM
Room: 160 MATH ANNEX
Chair: TIMOTHY STEIMLE, Arizona State University, Tempe, AZ
MF01
INVITED TALK
SEARCH FOR A VARIATION OF FUNDAMENTAL CONSTANTS
30 min 1:30
W. UBACHS, Department of Physics and Astronomy, VU University Amsterdam, De Boelelaan 1081, 1081
HV Amsterdam, Netherlands.
MF02
AN ALCOHOL TEST FOR DRIFTING CONSTANTS
15 min 2:05
P. JANSEN, J. BAGDONAITE, W. UBACHS and H.L. BETHLEM, Institute for Lasers, Life and Biophotonics, VU University Amsterdam, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands; I. KLEINER,
Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), CNRS UMR 7583 et Universités Paris
Diderot et Paris Est, 61 av. Général de Gaulle, 94010 Créteil Cédex, France; L.-H. XU, Department of
Physics and Centre for Laser, Atomic, and Molecular Sciences, University of New Brunswick, Saint John, New
Brunswick E2L 4L5, Canada.
MF03
15 min 2:22
SENSITIVITY OF TRANSITIONS IN INTERNAL ROTOR MOLECULES TO A POSSIBLE VARIATION OF THE
PROTON-TO-ELECTRON MASS RATIO
P. JANSEN, W. UBACHS, H. L. BETHLEM, Institute for Lasers, Life and Biophotonics, VU University
Amsterdam, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands; I. KLEINER, Laboratoire Interuniversitaire des Systèmes Atmosphériques, CNRS et Universités Paris Diderot et Paris Est, 61 av. Général de
Gaulle, 94010, Créteil, France; L-H. XU, Department of Physics and Centre for Laser, Atomic and Molecular
Sciences, University of New Brunswick, Saint John, New Brunswick E2L 4L5, Canada.
MF04
CH3 OH SUB-DOPPLER SPECTROSCOPY
15 min 2:39
GERMAN YU. GOLUBIATNIKOV, SERGEY P. BELOV and ALEXANDER V. LAPINOV, Institute of Applied Physics of RAS, 46 Ulyanov str., 603950 Nizhny Novgorod, Russia.
MF05
15 min 2:56
HIGH RESOLUTION MICROWAVE SPECTROSCOPY OF CH AS A SEARCH FOR VARIATION OF FUNDAMENTAL CONSTANTS
S. TRUPPE, R. J. HENDRICKS, S. K. TOKUNAGA, E. A. HINDS, M. R. TARBUTT, Centre for Cold Matter,
Blackett Laboratory, Imperial College London, London, SW7 2BW.
MF06
SUB-DOPPLER AND FTMW SPECTROSCOPY OF HC3 N ISOTOPOLOGUES
15 min 3:13
A.V. LAPINOV, G. YU. GOLUBIATNIKOV, Institute of Applied Physics of RAS, 46 Ulyanov str., 603950
Nizhny Novgorod, Russia; A. P. VELMUZHOV, Institute of Metalloorganic Chemistry of RAS, 49 Tropinin
str., 603950 Nizhny Novgorod, Russia; J.-U. GRABOW, Institute of Physical Chemistry and Electrochemistry,
Leibniz University of Hannover, Callinstrasse 3A, 30167 Hannover, Germany; and A. GUARNIERI, Technical
Faculty of Christian Albrecht University of Kiel, Kaiserstrasse 2, 24143 Kiel, Germany.
3
MF07
15 min 3:30
THE CO A-X SYSTEM FOR CONSTRAINING COSMOLOGICAL DRIFT OF THE PROTON-ELECTRON MASS
RATIO
M. L. NIU, E. J. SALUMBIDES, D. ZHAO, J. BAGDONAITE, Department of Physics and Astronomy, and
LaserLaB, VU University, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands; N. DE OLIVEIRA,
D. JOYEUX, L. NAHON, Synchrotron Soleil, Orme des Merisiers, St Aubin BP 48, 91192, GIF sur Yvette
cedex, France; R. W. FIELD, Department of Chemistry, Massachusetts Institute of Technology, Cambridge,
Massachusetts 02139, USA; and W. UBACHS, Department of Physics and Astronomy, and LaserLaB, VU
University, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands.
MF08
PRECISE MEASUREMENT OF
15 min 3:47
40
CaH VIBRATIONAL TRANSITION FREQUENCY
+
MASATOSHI KAJITA, Nat. Ins. Info. Comm. Tech., Koganei, Tokyo 184-8795, Japan; MINORI ABE, Dep.
of Chemistry, Tokyo Metro. Univ., Hachioji, Tokyo 192-0397, Japan.
MF09
15 min 4:04
PRECISE MEASUREMENT OF VIBRATIONAL TRANSITION FREQUENCY OF OPTICALLY TRAPPED
MOLECULES
MASATOSHI KAJITA, Nat. Ins. Info. Comm. Tech., Koganei, Tokyo 184-8795, Japan; GEETHA GOPAKUMAR,MINORI ABE, and MASAHIKO HADA, Dep. of Chemistry, Tokyo Metro. Univ., Hachioji, Tokyo
192-0397, Japan.
Intermission
MF10
15 min 4:36
TOWARDS MORE ACCURATE MEASUREMENTS OF THE IONIZATION ENERGY OF MOLECULAR HYDROGEN
D. SPRECHER, M. BEYER, J. LIU, and F. MERKT, ETH Zürich, Laboratorium für Physikalische Chemie,
Wolfgang-Pauli-Strasse 10, 8093 Zürich, Switzerland; E. SALUMBIDES, K. S. E. EIKEMA, W. UBACHS,
Department of Physics and Astronomy, Laser Centre, Vrije Universiteit, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands; CH. JUNGEN, Laboratoire Aimé Cotton, CNRS II, Bâtiment 505, Campus d’Orsay,
91405 Orsay Cedex, France.
MF11
NON-ADIABATIC ENERGIES OF THE HYDROGEN MOLECULE
15 min 4:53
KRZYSZTOF PACHUCKI, Faculty of Physics, University of Warsaw, Hoża 69, 00-681 Warsaw, Poland;
JACEK KOMASA, Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland.
MF12
QED EFFECTS IN H2
15 min 5:10
MF13
PRECISION MEASUREMENT OF THE IONIZATION ENERGY OF THE GK
MOLECULAR HYDROGEN.
15 min 5:27
1
Σ+
g
(v = 1, N = 1) STATE OF
M. BEYER, D. SPRECHER and F. MERKT, ETH Zürich, Laboratorium für Physikalische Chemie, WolfgangPauli-Strasse 10, 8093 Zürich, Switzerland.
4
MF14
QED TESTS AND SEARCH FOR NEW PHYSICS IN MOLECULAR HYDROGEN
15 min 5:44
E. J. SALUMBIDES, M. L. NIU, G. D. DICKENSON, K. S. E. EIKEMA, Department of Physics and Astronomy, and LaserLaB, VU University, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands; J. KOMASA,
Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland; K. PACHUCKI, Faculty of Physics, University of Warsaw, Hoża 69, 00-681 Warsaw, Poland; and W. UBACHS, Department of
Physics and Astronomy, and LaserLaB, VU University, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands.
5
MG. RADICALS AND IONS
MONDAY, JUNE 17, 2013 – 1:30 PM
Chair: CHRISTOPHER NEESE, The Ohio State University, Columbus OH
MG01
15 min 1:30
COMBINATION BANDS BETWEEN 2900 AND 3600 CM
−1
OF CYCLIC O4 CATION TRAPPED IN SOLID NEON
MARILYN E. JACOX and WARREN E. THOMPSON, Sensor Science Division, National Institute of Standards and Technology, Gaithersburg, MD 20899-8441.
MG02
15 min 1:47
FOURIER TRANSFORM FAR-INFRARED SPECTROSCOPY OF
CHROTRON SOLEIL
HN+
2
ON THE AILES BEAMLINE OF SYN-
O. PIRALIa , S. GRUETa , M. VERVLOET, Ligne AILES, Synchrotron SOLEIL, L’Orme des Merisiers SaintAubin, 91192 Gif sur Yvette Cedex - France.
a Also
at: Institut des Sciences Moléculaires d’Orsay, UMR 8214 CNRS-Université Paris-Sud, Bât. 210, 91405 Orsay cedex, France.
MG03
15 min 2:04
SUB-DOPPLER SPECTROSCOPY OF ND3 H ION IN THE NH STRETCHING MODE
+
CHIH-HSUAN CHANG, GRANT T. BUCKINGHAM , and DAVID J. NESBITT, JILA, National Institute of
Standards and Technology University of Colorado, and Department of Chemistry and Biochemistry University
of Colorado at Boulder, Colorado 80309.
MG04
15 min 2:21
INFRARED SPECTROSCOPY OF JET COOLED ND2 H+
2
MOLECULAR IONS: THE SYMMETRIC AND ANTISYM-
METRIC NH STRETCH MODES
CHIH-HSUAN CHANG and DAVID J NESBITT, JILA, National Institute of Standards and Technology University of Colorado, and Department of Chemistry and Biochemistry University of Colorado at Boulder, Colorado 80309.
MG05
15 min 2:38
PRECISION LASER SPECTROSCOPY OF
H+
3
HSUAN-CHEN CHEN, Institute of Photonics Technologies, National Tsing Hua University, Hsinchu 30013,
Taiwan; JIN-LONG PENG, Center for Measurement Standards, Industrial Technology Research Institute,
Hsinchu 30011, Taiwan; T. AMANO, Department of Chemistry and Department of Physics and Astronomy,
University of Waterloo, Waterloo, ON N2L 3G1, Canada; JOW-TSONG SHY, Institute of Photonics Technologies, National Tsing Hua University and Department of Physics, National Tsing Hua University, Hsinchu
30013, Taiwan.
MG06
SUB-DOPPLER SPECTROSCOPY OF
15 min 2:55
H+
3
JAMES N. HODGES, ADAM J. PERRY, BRIAN M. SILLER, Department of Chemistry, University of Illinois, Urbana, IL 61801; BENJAMIN J. MCCALL, Departments of Chemistry, Astronomy, and Physics, University of Illinois, Urbana, IL 61801.
6
MG07
HIGH PRECISION SPECTROSCOPY OF
15 min 3:12
CH+
5
USING NICE-OHVMS
JAMES N. HODGES, ADAM J. PERRY, Department of Chemistry, University of Illinois, Urbana, IL 61801;
BENJAMIN J. MCCALL, Departments of Chemistry, Astronomy, and Physics, University of Illinois, Urbana,
IL 61801.
MG08
15 min 3:29
INFRARED SPECTROSCOPY OF THE MASS 43 CATION: ACETYL CATION AND PROTONATED KETENE
JONATHAN D. MOSLEY and MICHAEL A. DUNCAN, University of Georgia, Athens, GA 30683.
MG09
15 min 3:46
UBIQUITOUS INTERSTELLAR MOLECULES WITH RADICALLY DIFFERENT CATION STRUCTURES: INFRARED SPECTROSCOPY OF FORMALDEHYDE AND METHANOL CATIONS
Intermission
MG10
15 min 4:15
THE CORONENE VIBRONIC STATES ABOVE THE FIRST IONIZATION POTENTIAL INVESTIGATED THROUGH
TPEPICO EXPERIMENTS
PH. BRECHIGNAC, C. FALVO, P. PARNEIX , T. PINO, O. PIRALI, Institut des Sciences Moléculaires
d’Orsay, CNRS UMR8214, Univ Paris-Sud, Bât 210, F91405 Orsay Cedex, France; G. GARCIA, L. NAHON,
Synchrotron SOLEIL, L’ Orme des Merisiers, St Aubin, B.P. 48, 91192 Gif sur Yvette, France; C. JOBLIN,
D. KOKKIN, A. BONAMMY, IRAP, Université de Toulouse [UPS], CNRS, Toulouse, France; G. MULAS,
INAF-Osservatorio Astronomico di Cagliari-Astrochemistry Group, Strada 54, Località Poggio dei Pini, I09012 Capoterra (CA), Italy.
MG11
MASS ANALYZED THRESHOLD IONIZATION OF LUTETIUM DIMER
15 min 4:32
LU WU, MOURAD ROUDJANE, YANG LIU AND DONG-SHENG YANG, Department of Chemistry, University of Kentucky, Lexington, KY 40506-0055.
MG12
C-C BOND ACTIVATION AND COUPLING OF PROPENE INDUCED BY LA ATOM
15 min 4:49
DILRUKSHI HEWAGE, Department of Chemistry, University of Kentucky, Lexington, KY 40506-0055;
HONG TAO, Department of Chemistry, Southwest Forestry University, Kunming 650224, PR China;
RUCHIRA SILVA, SUDESH KUMARI, AND DONG-SHENG YANG, Department of Chemistry, University of Kentucky, Lexington, KY 40506-0055.
MG13
HIGH-RESOLUTION PHOTOELECTRON SPECTROSCOPY OF 2-BUTYNE
15 min 5:06
UGO JACOVELLA, BÉRENGER GANS and FRÉDÉRIC MERKT, ETH Zürich, Laboratorium für
Physikalische Chemie, Wolfgang-Pauli-Strasse 10, 8093 Zürich, Switzerland.
7
MG14
15 min 5:23
UNDERSTANDING COMPLEX SPECTRAL SIGNATURES OF EMBEDDED EXCESS PROTONS IN MOLECULAR
SCAFFOLDS WITH THIRD ORDER CORRECTIONS TO THE HARMONIC POTENTIAL SURFACE
ANDREW F. DEBLASE and MARK A. JOHNSON, Yale University, P.O. Box 208107, New Haven, CT
06520, USA; THOMAS LECTKA, Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218, USA; XUN WANG and KENNETH D. JORDAN, University of Pittsburgh, 219 Parkman Avenue,
Pittsburgh, PA 15260, USA; ANNE B. McCOY, The Ohio State University, Columbus, Ohio 43210, USA.
MG15
SLOW ELECTRON VELOCITY-MAP IMAGING OF La2 (C6 H6 ) AND La(C6 H6 )2
15 min 5:40
RUCHIRA SILVA AND DONG-SHENG YANG, Department of Chemistry, University of Kentucky, Lexington, KY 40506-0055.
MG16
15 min 5:57
INFRARED SPECTROSCOPY AND STRUCTURES OF MASS-SELECTED RHODIUM CARBONYL AND
RHODIUM DINITROGEN CATIONS
HEATHER L. ABBOTT, Department of Chemistry and Biochemistry, Kennesaw State University, Kennesaw,
GA 30144; ANTONIO D. BRATHWAITE and MICHAEL A. DUNCAN, Department of Chemistry, University of Georgia, Athens, GA 30602-2256.
8
MH. MICROWAVE
MONDAY, JUNE 17, 2013 – 1:30 PM
Room: 1000 MCPHERSON LAB
Chair: ELANGANNAN ARUNAN, Indian Institute of Science, Bangalore, India
MH01
THE PROTOTYPE DIPEPTIDE GLY-GLY: A ROTATIONAL STUDY
15 min 1:30
M. VARELA, C. CABEZAS, S. MATA, J. L. ALONSO, Grupo de Espectroscopía Molecular (GEM), Edificio
Quifima, Laboratorios de Espectroscopía y Bioespectroscopía, Parque Científico, Universidad de Valladolid,
47011 Valladolid, Spain.
MH02
15 min 1:47
GAS-PHASE STRUCTURES OF LINALOOL AND COUMARIN STUDIED BY MICROWAVE SPECTROSCOPY
H. V. L. NGUYEN, W. STAHL, Institut für Physikalische Chemie, RWTH Aachen University, Landoltweg 2,
52074 Aachen, Germany; and J.-U. GRABOW, Institut für Physikalische Chemie und Elektrochemie, Lehrgebiet A, Callinstrasse 3-3a, 30167 Hannover, Germany.
MH03
MW SYSTEMATIC STUDY OF ALKALOIDS: THE DISTORTED TROPANE OF SCOPOLINE
10 min 2:04
PATRICIA ECIJA, EMILIO J. COCINERO, FRANCISCO J. BASTERRETXEA, JOSÉ A. FERNANDEZ,
FERNANDO CASTANO, Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Ap.644, E-48940, Bilbao, Spain; ALBERTO LESARRI, Departamento de
Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, E-47011 Spain.
MH04
15 min 2:16
STRUCTURAL STUDIES OF PYRROLE-BENZENE COMPLEXES BY CHIRPED-PULSE ROTATIONAL SPECTROSCOPY
SIMON LOBSIGER, CRISTOBAL PEREZ, DANIEL P. ZALESKI, NATHAN A. SEIFERT,
BROOKS H. PATE, Department of Chemistry, University of Virginia, McCormick Rd., Charlottesville,
VA 22904; CHANTAL PFAFFEN, MARIA A. TRACHSEL, SAMUEL LEUTWYLER, Departement für
Chemie und Biochemie, Universität Bern, Freiestrasse 3, 3012 Bern, Switzerland.
MH05
15 min 2:33
A “WET DOG" TUNNELING MOTION AS THE CAUSE FOR THE DOUBLED ROTATIONAL SPECTRUM OF 1IODONONAFLUOROBUTANE
W. C. BAILEY, Chemistry-Physics Department (Retired), Kean University, Union, New Jersey, USA 07083;
R. K. BOHN, Departments of Chemistry and Physics, University of Connecticut,Storrs, Connecticut, 062693060, USA.; G. S. GRUBBS II, Department of Chemistry, Wesleyan University, Hall-Atwater Laboratories,
52 Lawn Ave, Middletown, Connecticut, 06459-0180, USA.; Z. KISIEL, Institute of Physics, Polish Academy
of Sciences, Al. Lotnikóv 32146, 02-668 Warszawa, Poland.; S. A. COOKE, School of Natural and Social
Sciences, Purchase College SUNY, 735 Anderson Hill Road, Purchase, NY 10577, USA.
9
MH06
15 min 2:50
TORSIONAL SPLITTING IN THE ROTATIONAL SPECTRUM FROM 8 TO 650 GHz OF THE GROUND STATE OF
1,1-DIFLUOROACETONE
L. MARGULÈS, R. A. MOTIYENKO, Laboratoire de Physique des Lasers, Atomes, et Molécules, UMR
CNRS 8523, Université de Lille I, 59655 Villeneuve d’Ascq Cedex, France; P. GRONER, Department of
Chemistry, University of Missouri-Kansas City, 5100 Rockhill Road, Kansas City, MO 64110-2499, USA;
F. De CHIRICO, A. TURK, S. A. COOKE, School of Natural and Social Sciences, Purchase College SUNY,
735 Anderson Hill Road, Purchase, NY 10577, USA.
MH07
15 min 3:07
AN IMPROVED ANALYSIS OF THE SEVOFLURANE-BENZENE STRUCTURE BY CHIRPED PULSE FTMW
SPECTROSCOPY
NATHAN A. SEIFERT, CRISTOBAL PEREZ, DANIEL P. ZALESKI, JUSTIN L. NEILL, BROOKS H.
PATE, Department of Chemistry, University of Virginia, McCormick Rd., Charlottesville, VA 22904-4319;
ALBERTO LESARRI, MONTSERRAT VALLEJO, Departamento de Química Física y Química Inorgánica,
Facultad de Ciencias, Universidad de Valladolid, E-47011 Valladolid, Spain; EMILIO J. COCINERO, FERNANDO CASTANO, Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del
País Vasco (UPV/EHU), Campus de Leioa, Ap. 644, E-48080 Bilbao, Spain; ISABELLE KLEINER, Laboratorie Interuniversitaire des Systèmes Atmosphériques (LISA), CNRS et Universités Paris Est et Paris Diderot,
61. av Général de Gaulle, 94010 Créteil, France.
MH08
10 min 3:24
STRUCTURE DETERMINATION OF TWO STEREOISOMERS OF SEVOFLURANE DIMER BY CHIRPED PULSE
FTMW SPECTROSCOPY
País Vasco (UPV/EHU), Campus de Leioa, Ap. 644, E-48080 Bilbao, Spain.
Intermission
MH09
THE COMPLETE MOLECULAR GEOMETRY OF SALICYL ALDEHYDE FROM ROTATIONAL
SPECTROSCOPY
15 min 3:50
O. DOROSH, E. BIALKOWSKA-JAWORSKA, Z. KISIEL, L. PSZCZOLKOWSKI, Institute of Physics, Polish Academy of Sciences, Al. Lotników 32/46, 02-668 Warszawa, Poland; M. KANSKA, T. M. KRYGOWSKI,
Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warszawa, Poland; H. MAEDER, Institut für Physikalische Chemie, Christian-Albrechts-Universität zu Kiel, Olshausenstrasse 40, D-24098 Kiel,
Germany.
MH10
10 min 4:07
LABORATORY OBSERVATION OF THE ROTATIONAL SPECTRUM OF A POTENTIAL INTERSTELLAR SUGAR,
ERYTHROSE
I. PENA, C. CABEZAS, A. M. DALY, S. MATA, J. L. ALONSO, Grupo de Espectroscopía Molecular (GEM),
Edificio Quifima, Laboratorios de Espectroscopía y Bioespectroscopía, Parque Científico, Universidad de
Valladolid, 47011 Valladolid, Spain.
10
MH11
15 min 4:19
ALDOPENTOSES IN THE GAS PHASE: ROTATIONAL SPECTRA OF D-XYLOSE, D-ARABINOSE, D-LYXOSE
AND 2-DEOXY-D-RIBOSE
I. PENA, C. CABEZAS, A. M. DALY, C. BERMUDEZ, S. MATA, S. BLANCO, J. C. LOPEZ,
J. L. ALONSO, Grupo de Espectroscopía Molecular (GEM), Edificio Quifima, Laboratorios de Espectroscopía y Bioespectroscopía, Parque Científico, Universidad de Valladolid, 47011 Valladolid, Spain.
MH12
A ROTATIONAL STUDY OF D-MANNOSE AND D-GALACTOSE
15 min 4:36
I. PENA, A. M. DALY, C. CABEZAS, S. MATA, J. L. ALONSO, Grupo de Espectroscopía Molecular
(GEM), Edificio Quifima, Laboratorios de Espectroscopía y Bioespectroscopía, Parque Científico, Universidad de Valladolid, 47011 Valladolid, Spain.
MH13
UNVEILING THE SWEET CONFORMATIONS OF KETOHEXOSES
15 min 4:53
C. BERMUDEZ, I. PENA, C. CABEZAS, A. M. DALY, S. MATA, J. L. ALONSO, Grupo de Espectroscopía
Molecular (GEM), Edificio Quifima, Laboratorios de Espectroscopía y Bioespectroscopía, Parque Científico,
Universidad de Valladolid, 47011 Valladolid, Spain.
MH14
15 min 5:10
ELUCIDATING THE STRUCTURE OF SUGARS: MW SPECTROSCOPY COMBINED WITH ULTRAFAST UV LASER VAPORIZATION
EMILIO J. COCINERO, PATRICIA ECIJA, FRANCISCO J. BASTERRETXEA, JOSÉ A. FERNANDEZ,
FERNANDO CASTANO, Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV-EHU), Ap. 644, E-48080 Bilbao, Spain; ALBERTO LESARRI, Departamento
de Química-Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, E-47011 Spain;
JENS-UWE GRABOW, Institut für Physikalische Chemie, Lehrgebiet A, Universität Hannover, Callinstraße.
3A, D-30167 Hannover, Germany; ALVARO CIMAS, Laboratoire Analyse et Modélisation pour la Biologie
et l’Environnement, Université d’Évry val d’Essonne, F-91025 Evry (France).
MH15
15 min 5:27
TOWARDS SOLVATION OF A CHIRAL ALPHA-HYDROXY ESTER: BROADBAND CHIRP AND NARROW BAND
CAVITY FOUIRIER TRANSFORM MICROWAVE SPECTROSCOPY OF METHYL LACTATE-WATER CLUSTERS
JAVIX THOMAS, OLEKSANDR SUKHORUKOV, WOLFGANG JAEGER, YUNJIE XU, Department of
Chemistry, University of Alberta, Edmonton, AB, T6G 2G2, Canada.
11
MI. ELECTRONIC
MONDAY, JUNE 17, 2013 – 1:30 PM
Chair: DAMIEN FORTHOMME, Brookhaven National Lab, Upton, NY
MI01
15 min 1:30
A DPF ANALYSIS YIELDS QUANTUM MECHANICALLY ACCURATE ANALYTIC POTENTIAL ENERGY FUNCTIONS FOR THE A 1 Σ+ and X 1 Σ+ STATES OF NaH
ROBERT J. LE ROY, SADRU WALJI, KATHERINE SENTJENS, Department of Chemistry, University of
Waterloo, Waterloo, Ontario N2L 3G1, Canada.
MI02
15 min 1:47
UNCERTAINTIES IN PROPERTIES CALCULATED FROM FITTED POTENTIAL FUNCTIONS and DETERMINING
POTENTIAL FUNCTIONS FROM FITS TO BOUND → CONTINUUM INTENSITY DATA
ROBERT J. LE ROY, Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1,
Canada.
MI03
15 min 2:04
ASSIGNING COMPLEX VIBRATION-TUNNELING SPECTRA USING FRANCK-CONDON FINGERPRINTS
EDUARDO BERRIOS, PRAVEEN SUNDARADEVAN and MARTIN GRUEBELE, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Il 61801.
MI04
15 min 2:21
OPTICAL-OPTICAL DOUBLE RESONANCE AND LIF SPECTROSCOPY OF THE JET-COOLED BORON CARBIDE (BC) FREE RADICAL
FUMIE X. SUNAHORI, RAMYA NAGARAJAN, AND DENNIS J. CLOUTHIER, Department of Chemistry,
University of Kentucky, Lexington, KY 40506-0055.
MI05
10 min 2:38
REINVESTIGATION OF THE EMISSION SPECTRA FOLLOWING THE 266 NM PHOTOLYSIS OF
IODOMETHANES
CIAN-PING TU, HSIN-I CHENG, and BOR-CHEN CHANG, Department of Chemistry, National Central
University, 300 Jhongda Road, Jhongli 32001, Taiwan.
MI06
15 min 2:50
CAVITY RINGDOWN ABSORPTION SPECTRUM OF THE T1 (n, π ) ← S0 TRANSITION OF
2-CYCLOHEXEN-1-ONE
∗
KATHERINE L. ZABRONSKY, MICHAEL O. McANALLY, DANIEL J. STUPCA, NATHAN R. PILLSBURY, and STEPHEN DRUCKER, Department of Chemistry, University of Wisconsin-Eau Claire, Eau
Claire, WI 54702.
MI07
15 min 3:07
COMPUTATIONAL INVESTIGATION OF THE T1 (n, π ) STATE OF 2-CYCLOHEXEN-1-ONE
∗
MICHAEL O. McANALLY and STEPHEN DRUCKER, Department of Chemistry, University of WisconsinEau Claire, Eau Claire, WI 54702.
12
Intermission
MI08
15 min 3:40
PROBING COMPETITIVE NONCOVALENT INTERACTIONS: RESONANCE ENHANCED TWO-PHOTON IONIZATION (R2PI) SPECTROSCOPY OF HALOAROMATIC CLUSTERS
SILVER NYAMBO, LLOYD MUZANGWA, BRANDON UHLER AND SCOTT A. REID, Department of
Chemistry, Marquette University, Milwaukee, WI 53233.
MI09
NONLINEAR DUAL-COMB SPECTROSCOPY WITH TWO-PHOTON EXCITATION
15 min 3:57
S. A. MEEK, A. HIPKE, T. W. HÄNSCH, N. PICQUÉ, Max-Planck-Institut für Quantenoptik, HansKopfermann-Straße 1, D-85748 Garching, Germany.
MI10
15 min 4:14
NEW DEVELOPMENTS OF BROADBAND CAVITY ENHANCED SPECTROSCOPIC TECHNIQUES
A. WALSH, D. ZHAO, H. LINNARTZ, Sackler Laboratory for Astrophysics, Leiden Observatory, University
of Leiden, P.O. Box 9513, NL-2300 RA Leiden, the Netherlands; W. UBACHS, LaserLaB, VU University
Amsterdam, De Boelelaan 1081, NL-1081 HV, Amsterdam, The Netherlands.
MI11
15 min 4:31
MEASURING THE QUENCHING OF NO FLUORESCENCE PRODUCED FROM THE EXCITATION OF PHOTOFRAGMENTED NITROBENZENE USING A PICOSECOND LASER.
CHRISTOPHER J. LUE, CHAKREE TANJAROON, J. BRUCE JOHNSON, SCOTT W. REEVE, Arkansas
Center for Laser Applications and Science and Department of Chemistry and Physics, P.O. Box 419 State University, AR 72467; SUSAN D. ALLEN, Embry Riddle Aeronautical University, 600 S. Clyde Morris Boulevard, Daytona Beach, FL 32114.
MI12
SPECTROSCOPY OF LUMINESCENT CRYSTALS CONTAINING RARE EARTH ELEMENTS
15 min 4:48
MENG-LING CHEN, KWANG-HWA LII, and BOR-CHEN CHANG, Department of Chemistry, National
Central University, 300 Jhongda Road, Jhongli 32001, Taiwan.
MI13
DNA-ENHANCED DYE-SENSITIZED SOLAR CELLS
15 min 5:05
MARVIN POLLUM and CARLOS E. CRESPO-HERNÁNDEZ, Department of Chemistry and Center for
Chemical Dynamics, Case Western Reserve University, Cleveland, Ohio 44106.
MI14
15 min 5:22
SIMULATION OF FREE→FREE ABSORPTION SPECTRA AND THE CALCULATION OF INTERACTION POTENTIALS FOR ALKALI-RARE GAS ATOM PAIRS
J. DARBY HEWITT, THOMAS M. SPINKA, JASON. D. READLE, and J. GARY EDEN,
Laboratory for Optical Physics and Engineering
University of Illinois at Urbana Champaign
Champaign, IL 61820.
13
MI15
SPECTROSCOPY OF 1,2-DIPHENYLETHANE-(H2O)n (n=1-3) CLUSTERS
15 min 5:39
JOSEPH R. GORD, EVAN G. BUCHANAN, PATRICK S. WALSH, and TIMOTHY S. ZWIER, Department
of Chemistry, Purdue University, West Lafayette. IN 47907.
MI16
15 min 5:56
TROPOLONE COMPLEXES FORMED WITH AMPHOTERIC LIGANDS: STRUCTURE AND DYNAMICS AS
VIEWED ACROSS THE VIBRONIC LANDSCAPE
DEACON J. NEMCHICK, KATHRYN CHEW, and PATRICK H. VACCARO, Department of Chemistry, Yale
University, P.O. Box 20817, New Haven, CT 06520-8107 USA.
14
MJ. ATMOSPHERIC SPECIES
MONDAY, JUNE 17, 2013 – 1:30 PM
Chair: CHRIS MCRAVEN, Brookhaven National Lab, Upton, NY
MJ01
WATER BROADENING OF OXYGEN
15 min 1:30
BRIAN J. DROUIN, VIVIENNE PAYNE, Jet Propulsion Laboratory, California Institute of Technology,
4800 Oak Grove Dr., Pasadena, CA 91109; ELI MLAWER, Atmospheric and Environmental Research, 131
Hartwell Avenue, Lexington, MA 02421.
MJ02
LINE PARAMETERS FOR THE OXYGEN A BAND
15 min 1:47
D. CHRIS BENNER, V. MALATHY DEVI, JIAJUN HOO, Department of Physics, College of William and
Mary, Williamsburg, VA; KEEYOON SUNG, Jet Propulsion Laboratory, California Institute of Technology,
Pasadena, CA; JOSEPH T. HODGES, DAVID A. LONG, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD; THINH BUI, PRIYANKA MILINDA RUPASINGHE,
MITCHIO OKUMURA, California Institute of Technology, Pasadena, CA.
MJ03
AIR-BROADENING AND SHIFT PARAMETERS IN THE ν3 BAND OF OZONE
15 min 2:04
M. A. H. SMITH, Science Directorate, NASA Langley Research Center, Hampton, VA 23681-2199;
V. MALATHY DEVI and D. CHRIS BENNER, Department of Physics, The College of William and Mary,
Williamsburg, VA 23187-8795.
MJ04
15 min 2:21
AIR-BROADENED LINE SHAPES IN THE 2ν3 R BRANCH OF
12
CH4 BETWEEN 6014 AND 6100 CM−1
V. MALATHY DEVI, D. CHRIS BENNER, Dept. of Physics, The College of William and Mary, Williamsburg, VA 23187; K. SUNG, L. R. BROWN, T. J. CRAWFORD, SHANSHAN YU, Jet Propulsion Laboratory,
California Institute of Technology, Pasadena, CA 91109; M. A. H. SMITH, Science Directorate, NASA Langley Research Center, Hampton, VA 23681; A. W. MANTZ, Dept. of Physics, Astronomy and Geophysics,
Connecticut College, New London, CT 06320.
MJ05
15 min 2:38
LINE BROADENING PARAMETERS OF METHANE AT 6000 CM
−1
VICTOR GORSHELEV, ANNA SERDYUCHENKO, M.BUCHWITZ, J.BURROWS, Insitute of Environmental Physics, University of Bremen, Germany; NEIL HUMPAGE, J. REMEDIOS, Earth Observation Science Group, University of Leicester, UK.
MJ06
EXAMINING CONTRIBUTIONS TO LINE SHAPES IN THE ν1 + ν3 BAND OF ACETYLENE
15 min 2:55
MATTHEW J. CICH, SALVATORE M. CAIOLA, STEPHEN W LEE, GARY V. LOPEZ, TREVOR J.
SEARSa , Department of Chemistry, Stony Brook University, Stony Brook, New York 11794; DAMIEN
FORTHOMME, C. P. MCRAVEN, GREGORY E. HALL, Department of Chemistry, Brookhaven National
Laboratory, Upton, New York 11973; A. W. MANTZ, Department of Physics, Astronomy, and Astrophysics,
a also:
Department of Chemistry, Brookhaven National Laboratory, Upton, New York 11973
15
Intermission
MJ07
15 min 3:30
REFINEMENT OF THE ROBERT-BONAMY FORMALISM: TAKING INTO ACCOUNT OF CONTRIBUTIONS
FROM THE LINE COUPLING
Q. MA, NASA/Goddard Institute for Space Studies and Department of Applied Physics and Applied Mathematics, Columbia University, 2880 Broadway, New York, NY 10025; C. BOULET, Institut des Sciences
Moléculaires d’Orsay (ISMO); CNRS (UMR8214) et Université Paris-Sud Bât 350 Campusd’Orsay F-91405
FRANCE; R. H. TIPPING, Department of Physics and Astronomy, University of Alabama, Tuscaloosa, AL
35487.
MJ08
UNDISCOVERED ERRORS OF VOIGT PROFILE BEYOND TINY W-SHAPED RESIDUALS
15 min 3:47
G. WAGNER, M. BIRK, DLR, D-82234 Wessling, Germany; S.A. CLOUGH, Clough Radiation Associates,
89 Hancock Street, Lexington, MA 02420, USA.
MJ09
WATER INTENSITIES: AB INITIO VS. EXPERIMENT
15 min 4:04
MANFRED BIRK , GEORG WAGNER, DLR, D-82234 Wessling, Germany; LORENZO LODI,
JONATHAN TENNYSON, Department of Physics and Astronomy, University College London, London
WC1E 6BT, UK.
MJ10
FT-IR MEASUREMENTS OF CROSS SECTIONS OF COLD C3 H8 IN THE 7 - 15 µm FOR TITAN
15 min 4:21
KEEYOON SUNG, GEOFFREY C. TOON, LINDA R. BROWN, Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Dr.,Pasadena, CA 91109; ARLAN W. MANTZ, Dept. of Physics,
Connecticut College, New London, CT 06320; MARY ANN H. SMITH, Science Directorate, NASA Langley
Research Center, Hampton, VA 23681.
MJ11
15 min 4:38
QUANTITATIVE MEASUREMENT OF INTEGRATED BAND INTENSITIES OF ISOPRENE AND FORMALDEHYDE
CAROLYN S. BRAUER, TIMOTHY J. JOHNSON, THOMAS A. BLAKE, ROBERT L. SAMS, Pacific
Northwest National Laboratory, P. O. Box 999, Mail Stop K3-59, Richland, WA 99352.
MJ12
15 min 4:55
QUANTITATIVE INTENSITY STUDIES OF THREE GAS-PHASE MONOTERPENES IN THE INFRARED: αPINENE, β-PINENE AND D-LIMONENE
MJ13
10 min 5:12
COMPARISON OF EXPERIMENTAL AND THEORETICAL ABSORPTION CROSS SECTIONS OF PFBAm
PAUL J. GODIN, STEPHANIE CONWAY, Department of Physics, University of Toronto, 60 St. George St.,
Toronto, ON, M5S 1A7, Canada; ANGELA HONG, Department of Chemistry, University of Toronto, 80
St. George St., Toronto, ON, M5S 3H6, Canada; KARINE LE BRIS, Department of Physics, St. Francis
Xavier University, Antigonish, Nova Scotia, B2G 2W5, Canada; SCOTT MABURY, Department of Chemistry, University of Toronto, 80 St. George St., Toronto, ON, M5S 3H6, Canada; and KIMBERLY STRONG,
Department of Physics, University of Toronto, 60 St. George St., Toronto, ON, M5S 1A7, Canada.
16
MJ14
15 min 5:24
INVESTIGATING ATMOSPHERIC OXIDATION WITH MOLECULAR DYNAMICS IMAGING AND SPECTROSCOPY
W. G. MERRILL, A. S. CASE, and F. N. KEUTSCH, Department of Chemistry, University of Wisconsin,
Madison, WI 53706.
MJ15
10 min 5:41
PHOTODISSOCIATION DYNAMICS OF 2-BROMOETHYLNITRITE AT 351 NM AND C-C BOND FISSION IN THE
β-BROMOETHOXY RADICAL PRODUCT
LEI WANG, Department of Chemistry, The University of Chicago, Chicago, IL 60637; RABI CHHANTYALPUN, Department of Chemistry, The Ohio State University, Columbus, OH 43210; MATT D. BRYNTESON,
Department of Chemistry, The University of Chicago, Chicago, IL 60637; TERRY A. MILLER, Department
of Chemistry, The Ohio State University, Columbus, OH 43210; and LAURIE J. BUTLER, Department of
Chemistry, The University of Chicago, Chicago, IL 60637.
MJ16
PHOTOCHEMISTRY OF ACETONE IN SIMULATED ATMOSPHERE
15 min 5:53
T. CHAKRABORTY, A. K. GHOSH and A. CHATTOPADHYAY, Department of Physical Chemistry, Indian
Association for the cultivation of science, Calcutta 700032, India. E-mail: [email protected].
17
MK. INFRARED/RAMAN
MONDAY, JUNE 17, 2013 – 1:30 PM
Room: 1153 SMITH LAB
Chair: JENNIFER VAN WIJNGAARDEN, University of Manitoba, Winnipeg MB, Canada
MK01
15 min 1:30
ROTATIONALLY-RESOLVED SPECTROSCOPY OF THE BENDING MODES OF DEUTERATED WATER DIMER
JACOB T. STEWART, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL
61801; BENJAMIN J. McCALL, Departments of Chemistry and Astronomy, University of Illinois at UrbanaChampaign, Urbana, IL 61801.
MK02
15 min 1:47
INFRARED SPECTROSCOPY OF ((CH3 )3 N)n -H -H2 O (n=1-3): STRUCTURES AND DISSOCIATION CHANNELS
OF PROTONATED MIXED CLUSTERS AROUND A MAGIC NUMBER
+
RYUNOSUKE SHISHIDO, ASUKA FUJII, Department of Chemistry, Graduate School of Science, Tohoku
University, Sendai 980-8578, Japan; JER-LAI KUO, Institute of Atomic and Molecular Science, Academia
Sinica, Taipei 10617, Taiwan.
MK03
15 min 2:04
MAPPING CONFORMATIONAL ENERGY BARRIERS IN HYDRATED RUBIDIUM ION CLUSTERS
HAOCHEN KE, AMY L. NICELY, JAMES M. LISY, Department of Chemistry, University of Illinois at
Urbana-Champaign, Urbana, IL 61801.
MK04
15 min 2:21
IR SPECTROSCOPY OF [Ag·(CO2 )n ]− CLUSTERS: IMPLICATIONS FOR REDUCTIVE ACTIVATION OF CO2
BENJAMIN J. KNURR and J. MATHIAS WEBER, JILA and Department of Chemistry and Biochemistry,
University of Colorado, Boulder, CO 80309.
MK05
HIGH-RESOLUTION INFRARED SPECTROSCOPY OF Ge2 C3
15 min 2:38
S. THORWIRTH, V. LUTTER, S. SCHLEMMER, I. Physikalisches Institut, Universität zu Köln, 50937 Köln,
Germany; T. F. GIESEN, Universität Kassel, Fachbereich 10 - Physik, 34132 Kassel, Germany; J. GAUSS,
Institut für Physikalische Chemie, Universität Mainz, 55099 Mainz, Germany.
MK06
FIRST OBSERVATION OF CO TRIMER AND A NEW LOOK AT CO DIMER
15 min 2:55
M. REZAEI, S. SHEYBANI-DELOUI, N. MOAZZEN-AHMADI, Department of Physics and Astronomy,
University of Calgary, 2500 University Dr., N.W., Calgary, AB T2N 1N4, Canada; K.H. MICHAELIAN,
Natural Resources Canada, CanmetENERGY, 1 Oil Patch Drive, Suite A202, Devon, AB T9G 1A8, Canada;
A.R.W. McKELLAR, National Research Council of Canada, Ottawa, ON K1A 0R6, Canada.
18
MK07
15 min 3:12
OBSERVATION OF COMBINATION BANDS INVOLVING INTERMOLECULAR VIBRATIONS OF N2 O-N2 , N2 OOCS AND N2 O-CO2 COMPLEXES USING AN EXTERNAL CAVITY QUANTUM CASCADE LASER
University of Calgary, 2500 University Dr., N.W., Calgary, Alberta T2N 1N4, Canada; A.R.W. McKELLAR,
National Research Council of Canada, Ottawa, Ontario, K1A 0R6, Canada.
MK08
INFRARED SPECTRA OF THE NE2 -N2 O, AR2 -N2 O TRIMERS
15 min 3:29
M. REZAEI, N. MOAZZEN-AHMADI, Department of Physics and Astronomy, University of Calgary, 2500
University Dr., N.W., Calgary, Alberta T2N 1N4, Canada; K.H. MICHAELIAN, Natural Resources Canada,
CanmetENERGY, 1 Oil Patch Drive, Suite A202 Devon, Alberta, T9G 1A8, Canada; A.R.W. McKELLAR,
Intermission
MK09
15 min 4:00
INFRARED SPECTRUM OF THE (CO2 )2 -N2 O TRIMER MEASURED IN N2 O ν1 AND ν3 REGIONS.
J. NOROOZ OLIAEE, N. MOAZZEN-AHMADI, Department of Physics and Astronomy, University of Calgary, 2500 University Dr., N.W., Calgary, Alberta T2N 1N4, Canada; A.R.W. McKELLAR, National Research
Council of Canada, Ottawa, Ontario, K1A 0R6, Canada.
MK10
OBSERVATION OF A PLANAR ISOMER OF THE N2 O-(C2 H2 )2 TRIMER
15 min 4:17
S. SHEYBANI-DELOUI, J. NOROOZ OLIAEE, M. REZAEI, N. MOAZZEN-AHMADI, Department of
Physics and Astronomy, University of Calgary, 2500 University Drive North West, Calgary, Alberta, Canada
T2N 1N4; A.R.W. McKELLAR, National Research Council of Canada, Ottawa, Ontario, Canada K1A 0R6.
MK11
15 min 4:34
INFRARED SPECTRUM OF THE CS2 TETRAMER: OBSERVATION OF A STRUCTURE WITH D2d SYMMETRY
M. REZAEI, J. NOROOZ OLIAEE, N. MOAZZEN-AHMADI, Department of Physics and Astronomy, University of Calgary, 2500 University Dr., N.W., Calgary, Alberta T2N 1N4, Canada; A.R.W. McKELLAR,
MK12
15 min 4:51
INFRARED SPECTROSCOPIC STUDY ON FERMI RESONANCE OF THE EXCESS PROTON VIBRATION IN BINARY CLUSTERS
University, Sendai 980-8578, Japan; JER-LAI KUO, Institute of Atomic and Molecular Sciences Academia
MK13
15 min 5:08
THEORETICAL STUDY ON FERMI RESONANCE OF THE EXCESS PROTON VIBRATION IN BINARY CLUSTERS
JER-LAI KUO, JAKE TAN, Institute of Atomic and Molecular Sciences Academia Sinica, Taipei 10617, Taiwan; RYUNOSUKE SHISHIDO, ASUKA FUJII, Department of Chemistry, Graduate School of Science,
Tohoku University, Sendai 980-8578, Japan.
19
MK14
10 min 5:25
MUTUAL CO-ASSIGNMENT OF THE CALCULATED VIBRATIONAL FREQUENCIES IN THE GROUND AND
LOWEST EXCITED ELECTRONIC STATES
YURII N. PANCHENKO, Laboratory of Molecular Spectroscopy, Division of Physical Chemistry, Department of Chemistry, Lomonosov Moscow State University, Moscow 119991, Russian Federation..
20
TA. MINI-SYMPOSIUM: SPECTROSCOPY TESTS OF FUNDAMENTAL
PHYSICS
TUESDAY, JUNE 18, 2013 – 8:30 AM
Chair: ANATOLY TITOV, St. Petersburg Nuclear Physics Institute, Gatchina, Russia
TA01
INVITED TALK
30 min 8:30
TOWARDS THE FIRST MEASUREMENT OF PARITY VIOLATION IN CHIRAL MOLECULES EW ATTEMPTS
AND FUTURE PROSPECTIVE
PETER SCHWERDTFEGER, Centre for Theoretical Chemistry and Physics, The New Zealand Institute for
Advanced Study, Massey University Auckland, Auckland, New Zealand.
TA02
15 min 9:05
RIGOROUS RELATIVISTIC METHODS FOR ADDRESSING P- AND T -NONCONSERVATION IN HEAVYELEMENT MOLECULES
TIMO FLEIG, Laboratoire de Chimie et Physique Quantiques, Université Paul Sabatier Toulouse 3, Toulouse,
France.
TA03
15 min 9:22
PARITY VIOLATION IN CHIRAL MOLECULES: CURRENT STATUS OF THEORY AND SPECTROSCOPIC EXPERIMENT
MARTIN QUACK, GEORG SEYFANG, Physical Chemistry, ETH Zurich, CH-8093 Zurich, Switzerland.
TA04
15 min 9:39
A COMBINED SYNCHROTRON-BASED HIGH RESOLUTION FTIR AND DIODE LASER JET INFRARED SPECTROSCOPY STUDY OF THE CHIRAL MOLECULE CDBrClF
S. ALBERT, K. KEPPLER ALBERT, M. QUACK, PHYSICAL CHEMISTRY, ETH ZÜRICH, CH-8093
ZÜRICH, SWITZERLAND; PH. LERCH, SWISS LIGHT SOURCE, PAUL-SCHERRER-INSTITUTE, CH-5232
VILLIGEN, SWITZERLAND ; V. BOUDON, LABORATOIRE CARNOT DE BOURGOGNE, UNIVERSITE DE
BOURGOGNE, F-21078 DIJON, FRANCE.
TA05
CAVITY-ENHANCED PARITY-NONCONSERVING OPTICAL ROTATION IN Hg, Xe, AND I
15 min 9:56
L. BOUGAS, G. E. KATSORINAKIS, T. PETER RAKITZIS, Department of Physics, University of Crete, and
Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas 71110 HeraklionCrete, Greece.
TA06
15 min 10:13
CHIRAL CAVITY RING-DOWN: ABSOLUTE MEASUREMENT OF OPTICAL ROTATION IN GASES AND LIQUIDS WITH SIGNAL REVERSALS
LYKOURGOS BOUGAS, G. E. KATSOPRINAKIS, T. P. RAKITZIS, Department of Physics, University of
Crete, and Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas 71110
Heraklion-Crete, Greece.
21
Intermission
TA07
15 min 10:45
NEW PERSPECTIVES ON THE SEARCH FOR A PARITY VIOLATION EFFECT IN CHIRAL MOLECULES
F. AUGUSTE, S. K. TOKUNAGA, A. SHELKOVNIKOV, C. DAUSSY, A. AMY-KLEIN, C. CHARDONNET and B. DARQUIÉ, Laboratoire de Physique des Lasers, Université Paris 13, Sorbonne Paris Cité, CNRS,
F-93430, Villetaneuse, France.
TA08
TRAVELLING-WAVE DECELERATION OF HEAVY DIATOMIC MOLECULES
15 min
11:02
J. E. VAN DEN BERG, C. MEINEMA, S. MATHAVAN, S. HOEKSTRA, University of Groningen, Zernikelaan 25, 9747 AA, Groningen, The Netherlands.
TA09
DETECTING PARITY VIOLATION USING TRAPPED MOLECULES
15 min
11:19
TA10
A SLOW SOURCE OF MOLECULES FOR HIGH RESOLUTION SPECTROSCOPY
15 min
11:36
MARINA QUINTERO-PÉREZ, PAUL JANSEN, THOMAS E. WALL, WIM UBACHS and HENDRICK L. BETHLEM, LaserLaB, Department of Physics and Astronomy, VU University Amsterdam, De
Boelelaan 1081, 1081 HV Amsterdam, The Netherlands.
TA11
15 min 11:53
NOVEL INFRARED COHERENT SOURCES AND TECHNIQUES FOR SPECTROSCOPIC TEST OF FUNDAMENTAL PHYSICS PRINCIPLES
P. CANCIO PASTOR, I. GALLI, G. GIUSFREDI, D. MAZZOTTI, and P. DE NATALE, Istituto Nazionale
di Ottica-Consiglio Nazionale delle Ricerche (INO-CNR), and European Laboratory for Non-linear Spectroscopy (LENS) Via N. Carrara 1, 50019 Sesto Fiorentino, Italy.
22
TB. MINI-SYMPOSIUM: SPECTROSCOPY OF PLANETARY
ATMOSPHERES
Chair: PETER BERNATH, Old Dominion University, Norfolk, Virginia
TB01
INVITED TALK
30 min 8:30
THE ROLE OF SPECTROSCOPY IN RESEARCH ON THE NEUTRAL ATMOSPHERES OF THE OUTER SOLAR
SYSTEM
GLENN S. ORTON, JET PROPULSION LABORATORY, CALIFORNIA INSTITUTE OF TECHNOLOGY,
PASADENA, CA 91109.
TB02
INTENSITY MODELING OF METHANOL IN THE TORSIONAL MANIFOLD
15 min 9:05
LI-HONG XU, Centre for Laser, Atomic and Molecular Sciences (CLAMS), Physics Department, University
of New Brunswick, 100 Tucker Park Road, Saint John, NB, Canada E2L 4L5; ISABELLE KLEINER, Laboratoire Interuniversitaire des Systemes Atmosphériques, CNRS et Universités Paris Diderot et Paris Est, 61 av.
Général de Gaulle, 94010, Créteil, France.
TB03
THZ SPECTROSCOPY OF DEUTERATED ETHANE
15 min 9:22
BRIAN J. DROUIN, SHANSHAN YU, JOHN C. PEARSON, LINDA R. BROWN, KEEYOON SUNG, Jet
Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Dr., Pasadena, CA 91109; PETER
GRONER, Department of Chemistry, University of Missouri-Kansas City, Kansas City, MO 64110-2499.
TB04
15 min 9:39
OZONE RECOVERY IN THE PRESENCE OF O2 (a ∆) FOR ATMOSPHERIC STUDIES
1
MICHAEL C. HEAVEN, Department of Chemistry, Emory University, Atlanta, GA 30322; VALERIY N.
AZYAZOV, P.N. Lebedev Physical Institute, Samara Branch, Samara, Russia, 443029.
Intermission
TB05
Journal of Molecular Spectroscopy Review Lecture
30 min
10:15
EXOMOL: MOLECULAR LINE LISTS FOR EXOPLANET AND OTHER ATMOSPHERES
JONATHAN TENNYSON, Department of Physics and Astronomy, University College London, London,
WC1E 6BT, UK.
TB06
15 min
A NEW GLOBAL FIT FOR
17
10:50
O ENRICHED CO2
BEN M. ELLIOTT, CHARLES E. MILLER, Jet Propulsion Laboratory, California Institute of Technology,
4800 Oak Grove Drive, M/S 233-300, Pasadena, CA 91109.
23
TB07
15 min
SEMI-EMPIRICAL DIPOLE MOMENT FUNCTION OF X Σ CO
1
+
11:07
a
GANG LI, IOULI E. GORDON and LAURENCE S. ROTHMAN, Harvard-Smithsonian Center for Astrophysics, Atomic and Molecular Physics Division, Cambridge MA 02138, USA.
a This
effort has been supported by NASA through EOS grant NNX11AF91G and Planetary Atmospheres grant NNX10AB94G.
TB08
15 min
CHARACTERIZATION OF OZONE PROFILES DERIVED FROM AURA TES AND OMI RADIANCES
11:24
DEJIAN FU, JOHN R. WORDEN, SUSAN S. KULAWIK, KEVIN V. BOMAN AND VIJAY NATRAJ,
Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109; XIONG LIU, HarvardSmithsonian Center for Astrophysics, Cambridge, Massachusetts 02138, USA.
TB09
15 min 11:41
MODELING THE SPECTRUM OF THE 2ν2 and ν4 STATES OF AMMONIA TO EXPERIMENTAL ACCURACY
JOHN C. PEARSON, SHANSHAN YU, Jet Propulsion Laboratory, California Institute of Technology, 4800
Oak Grove Dr., Pasadena, CA 91109, USA.
24
TC. MICROWAVE
Chair: VADIM ILYUSHIN, Institute of Radio Astronomy NASU, Khazkov, Ukraine
TC01
10 min 8:30
ROTATIONAL SPECTRA AND ANALYSIS OF THE ARGON-MONOFLUOROPYRIDINE VAN DER WAALS COMPLEXES
MAHDI KAMAEE, MING SUN AND JENNIFER VAN WIJNGAARDEN, Department of Chemistry, University of Manitoba, Winnipeg MB R3T 2N2 Canada.
TC02
15 min 8:42
BROADBAND CHIRPED-PULSE FOURIER TRANSFORM MICROWAVE SPECTROSCOPY AND MOLECULAR
STRUCTURE OF THE ARGON-1-CHLORO-1-FLUOROETHYLENE COMPLEX
MARK D. MARSHALL AND HELEN O. LEUNG, Department of Chemistry, Amherst College, P.O. Box
5000, Amherst, MA 01002-5000.
TC03
15 min 8:59
MICROWAVE SPECTRA AND MOLECULAR STRUCTURES OF 2-CHLORO-1,1-DIFLUOROETHYLENE AND ITS
COMPLEX WITH ARGON
JOSEPH P. MESSINGER, GREGORY S. KNOWLTON, KATHRYN M. SUNDHEIM, HELEN O. LEUNG,
AND MARK D. MARSHALL, Department of Chemistry, Amherst College, P.O. Box 5000, Amherst, MA
01002-5000.
TC04
15 min 9:16
ROTATIONAL SPECTRA OF THE TRIFLUORO ETHANOL (TFE) -WATER CLUSTERS AND THE TFE DIMERS
JAVIX THOMAS, YUNJIE XU, Department of Chemistry, University of Alberta, Edmonton, AB, T6G 2G2,
Canada.
TC05
15 min 9:33
STRUCTURE FOR THE PROPIOLIC ACID - FORMIC ACID COMPLEX FROM MICROWAVE SPECTRA FOR
MULTIPLE ISOTOPOLOGUES a
STEPHEN G. KUKOLICH, ERIK G. MITCHELL, SPENCER J. CAREY, MING SUN, and
BRYAN M. SARGUS, Department of Chemistry and Biochemistry, The University of Arizona, Tucson,
Arizona 85721..
a Supported
by THE NATIONAL SCIENCE FOUNDATION
TC06
15 min 9:50
THE EFFECT OF PROTIC ACID IDENTITY ON THE STRUCTURES OF COMPLEXES WITH VINYL CHLORIDE:
FOURIER TRANSFORM MICROWAVE SPECTROSCOPY AND MOLECULAR STRUCTURE OF THE VINYL
CHLORIDE-ACETYLENE COMPLEX
HELEN O. LEUNG, MARK D. MARSHALL, AND FAN FENG, Department of Chemistry, Amherst College,
P.O. Box 5000, Amherst, MA 01002-5000.
25
Intermission
TC07
15 min 10:20
THE MICROWAVE STUDIES OF GUAIACOL (2-METHOXYPHENOL) ISOTOPOLOGUES AND VAN DER WAALS
COMPLEXES
RANIL M. GURUSINGHE, ASHLEY FOX, and MICHAEL J. TUBERGEN, Department of Chemistry, Kent
State University, Kent, OH 44242.
TC08
15 min 10:37
AN IMPROVED CHIRPED PULSE FTMW ANALYSIS OF THE STRUCTURES OF PHENOL DIMER AND TRIMER
NATHAN A. SEIFERT, CRISTÓBAL PÉREZ, AMANDA L. STEBER, DANIEL P. ZALESKI, JUSTIN L.
NEILL, BROOKS H. PATE, Department of Chemistry, University of Virginia, McCormick Rd., Charlottesville,
VA 22904-4319; ALBERTO LESARRI, Departamento de Química Física y Química Inorgánica, Facultad de
Ciencias, Universidad de Valladolid, E-47001 Valladolid, Spain.
TC09
10 min 10:54
OLIGOMERS BASED ON A WEAK HYDROGEN BOND NETWORK: THE ROTATIONAL SPECTRUM OF THE
TETRAMER OF DIFLUOROMETHANE
GANG FENG, LUCA EVANGELISTI, and WALTHER CAMINATI, Dipartimento di Chimica "G. Ciamician" dell’Università, Via Selmi 2, I-40126 Bologna, Italy; IVO CACELLI, and LAURA CARBONARO,
Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Risorgimento 35, I-56126 Pisa,
Italy; GIACOMO PRAMPOLINI, Istituto per i Processi Chimico-Fisici (IPCF-CNR), Area della Ricerca,
Via G. Moruzzi 1, I-56124 Pisa, Italy.
TC10
ROTATIONAL SPECTRA OF ADDUCTS OF FORMALDEHYDE WITH FREONS
15 min
11:06
GOU QIAN, GANG FENG, LUCA EVANGELISTI, and W. CAMINATI, Dipartimento di Chimica
"G. Ciamician" dell’Università, Via Selmi 2, I-40126 Bologna, Italy; MONTSERRAT VALLEJO LÓPEZ,
ALBERTO LESARRI, Departamento de Quimica Fisica y Quimica Inorganica, Facultad de Ciencias, Universidad de Valladolid, E-47011 Valladolid, Spain; EMILIO COCINERO, Departamento de Quimica Fisica,
Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco, E-48080 Bilbao, Spain.
TC11
MICROWAVE SPECTROSCOPIC INVESTIGATIONS
CH2 F2 · · · PROPYNE AND CH2 ClF· · · PROPYNE
OF
THE
C–H· · · π
15 min 11:23
CONTAINING COMPLEXES
REBECCA A. PEEBLES, SEAN A. PEEBLES, CORI L. CHRISTENHOLZ, ANTHONY A. ERNST, and
YASSER J. DHAHIR, Department of Chemistry, Eastern Illinois University, 600 Lincoln Ave., Charleston, IL
61920.
TC12
10 min 11:40
OBSERVATION OF A C–H· · · AROMATIC INTERACTION IN THE FLUOROBENZENE· · · HCCH WEAKLY
BOUND COMPLEX
NATHAN W. ULRICH, SEAN A. PEEBLES, REBECCA A. PEEBLES, and YASSER J. DHAHIR, Department of Chemistry, Eastern Illinois University, 600 Lincoln Ave., Charleston, IL 61920; NATHAN A.
SEIFERT, CRISTÓBAL PÉREZ, and BROOKS H. PATE, Department of Chemistry, University of Virginia,
McCormick Rd., PO Box 400319, Charlottesville, VA 22904.
26
TD. RADICALS AND IONS
Chair: YUAN-PERN LEE, National Chiao Tung University, Hsinchu, Taiwan
TD01
THE ROLES OF ATOMIC OXYGEN AND NITRIC OXIDE IN LOW TEMPERATURE PLASMAS
15 min 8:30
SHERRIE S. BOWMAN, DAVID BURNETTE, IGOR V. ADAMOVICH, and WALTER R. LEMPERT, M.A.
Chaszeyka Non-Equilibrium Thermodynamics Laboratory, The Ohio State University, Columbus, Ohio 43210..
TD02
15 min 8:47
SUB-DOPPLER SPECTROSCOPY OF trans-HOCO RADICAL IN THE OH STRETCHING MODE
CHIH-HSUAN CHANG, GRANT BUCKINGHAM, and DAVID J. NESBITT, JILA, National Institute of
TD03
15 min 9:04
e-X
e TRANSITION OF ISOPROPOXY RADICAL
VIBRONIC ANALYSIS FOR B
RABI CHHANTYAL-PUN and TERRY A. MILLER, Laser Spectroscopy Facility, Department of Chemistry,
The Ohio State University, 120 W. 18th Avenue, Columbus OH 43210.
TD04
15 min 9:21
ANALYSIS OF THE ROTATIONAL STRUCTURE OF B̃ 2 A′ ← X̃ 2 A′ TRANSITION OF ISOPROPOXY RADICAL:
ISOLATED STATE vs. COUPLED STATES MODEL
DMITRY G. MELNIK, and TERRY A. MILLER, Laser Spectroscopy Facility, Department of Chemistry, The
Ohio State University, 120 W. 18th Avenue, Columbus, Ohio 43210; JINJUN LIU, Department of Chemistry,
University of Louisville, 2320 South Brook Street, Louisville, Kentucky 40292.
TD05
15 min 9:38
HIGH-RESOLUTION LASER-INDUCED FLUORESCENCE SPECTROSCOPY OF CYCLOHEXOXY: ROTATIONAL
AND FINE STRUCTURE OF MOLECULES IN NEARLY DEGENERATE ELECTRONIC STATES
JINJUN LIU, Department of Chemistry, University of Louisville, 2320 S. Brook St., Louisville, Kentucky
40292.; DMITRY G. MELNIK, and TERRY A. MILLER, Laser Spectroscopy Facility, Department of Chemistry, The Ohio State University, 120 W. 18th Ave., Columbus, Ohio 43210.
TD06
15 min 9:55
ANOMALOUS Λ-DOUBLING IN THE INFRARED SPECTRUM OF THE HYDROXYL RADICAL IN HELIUM NANODROPLETS
P. RASTON, T. LIANG, and G. E. DOUBERLY, Department of Chemistry, University of Georgia, Athens,
Georgia 30602, USA.
27
TD07
15 min 10:12
HELIUM NANODROPLET ISOLATION SPECTROSCOPY AND AB INITIO CALCULATIONS OF HO3 -(O2 )N
CLUSTERS (N=0-4)
T. LIANG, P. RASTON, and G. E. DOUBERLY, Department of Chemistry, University of Georgia, Athens,
Georgia 30602, USA.
Intermission
TD08
15 min 10:45
FOURIER TRANSFORM INFRARED SPECTROSCOPY OF CH3 OO RADICAL IN MID-INFRARED RANGE
KUO-HSIANG HSU and YUAN-PERN LEE, Department of Applied Chemistry and Institute of Molecular
Science, National Chiao Tung University, Hsinchu 30010, Taiwan and Institute of Atomic and Molecular
Sciences, Academia Sinica, Taipei 10617; MENG HUANG and TERRY A. MILLER, Laser Spectroscopy
Facility, Department of Chemistry, The Ohio State University, 120 W. 18th Avenue, Columbus, Ohio 43210.
TD09
15 min
FARADAY ROTATION SPECTROSCOPY OF HO2 FROM AN ATMOSPHERIC FLOW REACTOR
11:02
BRIAN BRUMFIELD, GERARD WYSOCKI, Department of Electrical Engineering, Princeton University,
Princeton, NJ 08544; WENTING SUN, YIGUANG JU, Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544.
TD10
15 min
11:19
e−X
e ELECTRONIC TRANSITION OF C6 -C10 PEROXY RADICALS
OBSERVATION OF THE A
NEAL D. KLINE And TERRY A. MILLER, Laser Spectroscopy Facility, Department of Chemistry, The Ohio
State University, 120 W. 18th Avenue, Columbus, Ohio 43210..
TD11
15 min 11:36
STRUCTURE IN THE VISIBLE ABSORPTION BANDS OF JET-COOLED PHENYL PEROXY RADICALS
MICHAEL N. SULLIVAN, KEITH FREEL, J. PARK, M.C. LIN, and MICHAEL C. HEAVEN,
Department of Chemistry, Emory University, Atlanta, GA 30322.
TD12
TERAHERTZ ROTATIONAL SPECTROSCOPY OF THE SO RADICAL
15 min
11:53
M. A. MARTIN-DRUMEL, A. CUISSET, S. ELIET, G. MOURET, F. HINDLE, Laboratoire de PhysicoChimie de l’Atmosphère, EA 4493, Université du Littoral Côte d’Opale, 59140 Dunkerque, France; O. PIRALI, Institut des Sciences Moléculaires d’Orsay, CNRS, UMR 8214, Université Paris XI, bât. 210, 91405
Orsay Cedex, France; SOLEIL Synchrotron, AILES beamline, L’orme des Merisiers, Saint-Aubin, 91192 GifSur-Yvette, France.
28
TE. MATRIX/CONDENSED PHASE
Chair: MARILYN JACOX, NIST, Gaithersburg, MD
TE01
INFRARED SPECTROSCOPY OF HNO AND NOH SUSPENDED IN SOLID PARAHYDROGEN
15 min 8:30
DAVID T. ANDERSON AND MAHMUT RUZI, Department of Chemistry, University of Wyoming, Laramie,
WY 82071-3838.
TE02
COLD CHEMICAL REACTIONS OF H-ATOMS AND N2 O IN SOLID PARAHYDROGEN AT 2 K
DAVID T. ANDERSON AND FREDRICK M. MUTUNGA,
Wyoming, Laramie, WY 82071-3838.
15 min 8:47
Department of Chemistry, University of
TE03
15 min 9:04
RYDBERG STATES OF Rb AND Cs ATOMS ON HELIUM NANODROPLETS: A RYDBERG-RITZ
ANALYSIS
FLORIAN LACKNER, GÜNTER KROIS and WOLFGANG E. ERNST, Institute of Experimental Physics,
Graz University of Technology, Petersgasse 16, A-8010 Graz, Austria.
TE04
15 min 9:21
DYNAMICS OF CH3 F-(ortho-H2 )n CLUSTERS IN SOLID para-H2 CRYSTAL STUDIED BY PUMP AND PROBE
SPECTROSCOPY USING TWO CW-QUATUM CASCADE LASERS
H. KAWASAKI and A. MIZOGUCHI, H. KANAMORI, Department of Physics, Tokyo Institute of Technology, Tokyo, JAPAN 152-8551.
TE05
15 min 9:38
TERAHERTZ TIME DOMAIN SPECTROSCOPY OF SIMPLE ASTROPHYSICALLY RELEVANT ICES: THE
STRUCTURE OF THE ICE
SERGIO IOPPOLO, Division of Geological and Planetary Sciences, California Institute of Technology,
Pasadena, CA 91125; MARCO A. ALLODI, BRETT A. McGUIRE, MATTHEW J. KELLEY, Division of
Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125; GEOFFREY
A. BLAKE, Division of Chemistry and Chemical Engineering and Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125.
TE06
15 min 9:55
FIRST OBSERVATION OF A VIBRATIONAL FUNDAMENTAL OF SiC6 Si TRAPPED IN SOLID Ar
T.H. LE, C.M. L. RITTBY and W.R.M. GRAHAM, Department of Physics and Astronomy, Texas Christian
University, Fort Worth, TX 76129.
29
TE07
15 min 10:12
NIR LASER RADIATION INDUCED CONFORMATIONAL CHANGES AND TUNNELING LIFETIMES OF HIGHENERGY CONFORMERS OF AMINO ACIDS IN LOW-TEMPERATURE MATRICES
GABOR BAZSO, ESZTER E. NAJBAUER, GABOR MAGYARFALVI and GYORGY TARCZAY, Laboratory of Molecular Spectroscopy, Institute of Chemistry, Eotvos University, PO Box 32, H-1518, Budapest 112,
Hungary.
Intermission
TE08
15 min 10:45
CHARACTERIZATION OF A 1:1 METHANOL-BENZENE COMPLEX USING MATRIX ISOLATION INFRARED
SPECTROSCOPY
JAY C. AMICANGELO, NATALIE C. ROMANO, AND GEOFFREY R. DEMAY, School of Science, Penn
State Erie, Erie, PA 16563.
TE09
15 min 11:02
VUV PHOTOLYSIS OF NH3 : A MATRIX ISOLATION STUDY OF THE MOLECULAR INTERACTIONS BETWEEN
AMIDOGEN RADICAL AND AMMONIA MOLECULES
L. KRIM, and E. L. ZINS, Laboratoire de Dynamique, Interactions et Réactivité, LADIR, CNRS,UMR 7075,
Université Pierre et Marie Curie, 4 place Jussieu, 75252 Paris cedex 05, France.
TE10
HOT SPOT GENERATION IN ENERGETIC MATERIALS BY APPLYING WEAK ENERGIES
15 min
11:19
MING-WEI CHEN, SIZHU YOU, KENNETH S. SUSLICK, DANA D. DLOTT , School of Chemical Sciences, University of Illinois at Urbana-Champaign, Urbana, IL 61801.
TE11
THERMAL DECOMPOSITION MECHANISM OF BUTYRALDEHYDE
15 min
11:36
COURTNEY D. HATTEN, BRIAN WARNER, EMILY WRIGHT, KEVIN KASKEY, LAURA R. McCUNN,
Department of Chemistry, Marshall University, Huntington, WV 25755.
TE12
5 min 11:53
THE PECULIARITIES OF THE NMR SPIN-LATTICE RELAXATION IN PROTON EXCHANGED LINBO3
IGOR VERTEGEL, Institute of Physics NAS of Ukraine, Prospect Nauki 46, 03680 Kiev, Ukraine;
EUGENY CHESNOKOV, Institute of Physics NAS of Ukraine, Prospect Nauki 46, 03680 Kiev, Ukraine;
ALEXANDER OVCHARENKO, Institute of Physics NAS of Ukraine, Prospect Nauki 46, 03680 Kiev,
Ukraine; and IVAN VERTEGEL, The Faculty of Mechanics and Mathematics, National Taras Shevchenko
University of Kiev, Ukraine.
30
TF. MINI-SYMPOSIUM: SPECTROSCOPY TESTS OF FUNDAMENTAL
PHYSICS
TUESDAY, JUNE 18, 2013 – 1:30 PM
Chair: WIM UBACHS, Vrije Universiteit, Amsterdam, The Netherlands
TF01
AN OVERVIEW OF PNC RELATED STUDIES INVOLVING HEAVY POLAR MOLECULES
15 min 1:30
TIMOTHY C. STEIMLE , Department of Chemistry and Biochemistry, Arizona State University, Tempe,
AZ 85287.
TF02
15 min 1:47
ThF+ AS A CANDIDATE FOR eEDM MEASUREMENTS
MICHAEL C. HEAVEN, JOSHUA H. BARTLETT, Department of Chemistry, Emory University, Atlanta, GA
30322.
TF03
15 min 2:04
THE MOLECULAR FRAME ELECTRIC DIPOLE MOMENT AND HYPERFINE INTERACTIONS IN HAFNIUM
FLUORIDE, HfF
ANH LE AND TIMOTHY C. STEIMLE, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ 85287; LEONID SKRIPNIKOV AND ANATOLY V. TITOV, Petersburg Nuclear Physics
Institute, Gatchina, 188300, Russia and Quantum Mechanics Division, St. Petersburg State University, St.
Petersburg 198904, Russia.
TF04
15 min 2:21
A CONCEPT OF EFFECTIVE STATE OF ATOMS-IN-COMPOUNDS TO DESCRIBE PROPERTIES DETERMINED
BY THE VALENCE ELECTRON’S DENSITIES IN ATOMIC CORES
A.V. TITOV, Yu.V. LOMACHUK, L.V. SKRIPNIKOV, A.N. PETROV, N.S. MOSYAGIN a ,
B.P. Konstantinov Petersburg Nuclear Physics Institute, Gatchina, Leningrad district 188300;
Department of Physics, Saint Petersburg State University, Petrodvoretz 198904, RUSSIA.
a SPbU
Fundamental Science Research grant from Federal budget N 0.038.652.2013 and RFBR grant 13-02-01406 are gratefully acknowledged
TF05
15 min 2:38
VOLTAGE CONTROLLED GEOMETRIC PHASE ROTATION IN
208
Pb F.
19
J. E. FURNEAUX, NEIL SHAFER-RAY, J. COKER, P. M. RUPASINGHE„ Homer L. Dodge Department
of Physics and Astronomy, University of Oklahoma, Norman, OK 73019; and C. P. McRAVEN, Chemistry
Department, Brookhaven National Laboratory, Upton, NY 11973.
TF06
15 min 2:55
MEASUREMENT OF THE ELECTRON’S ELECTRIC DIPOLE MOMENT IN THORIUM MONOXIDE
J. BARON, Harvard University; D. DEMILLE, Yale University; J. DOYLE, G. GABRIELSE, P. HESS,
N. HUTZLER, Harvard University; B. OLEARY, Yale University; C. PANDA, E. PETRIK, B. SPAUN, Harvard Universitya .
a ACME
COLLABORATION
31
TF07
15 min 3:12
BROADBAND VELOCITY MODULATION SPECTROSCOPY OF MOLECULAR IONS FOR USE IN THE JILA
ELECTRON EDM EXPERIMENT
DANIEL N. GRESH, KEVIN C. COSSEL, ERIC A. CORNELL, and JUN YE, JILA, National Institute of
Standards and Technology and University of Colorado Department of Physics, University of Colorado, Boulder, Colorado 80309-0440, USA.
TF08
PROGRESS OF THE JILA ELECTRON EDM EXPERIMENT
15 min 3:29
HUANQIAN LOH, KEVIN C. COSSEL, MATT GRAU, DANIEL N. GRESH, KANG-KUEN NI, JUN YE,
and ERIC A. CORNELL, JILA, National Institute of Standards and Technology and University of Colorado
Department of Physics, University of Colorado, Boulder, Colorado 80309-0440, USA.
TF09
15 min 3:46
HYPERFINE INTERACTION IN DIATOMICS AS A TOOL FOR SUPPRESSION OF SYSTEMICS AND VERIFICATION OF THEORETICAL VALUES FOR THE EFFECTIVE ELECTRIC FIELD ON ELECTRON FOR THE ELECTRON EDM EXPERIMENTS
A.N. PETROV, L.V. SKRIPNIKOV, N.S. MOSYAGIN, A.V. TITOV a ,
a SPbU
TF10
15 min 4:03
ROTATIONAL SPECTRA IN SERVICE OF PARTICLE PHYSICS — ZEEMAN & HYPERFINE EFFECTS
RICHARD J MAWHORTER, ALEXANDER L. BAUM, ZACHARY GLASSMANN, BENJAMIN GIRODAS, Dept of Physics & Astronomy, Pomona College, Claremont, CA 91711; TREVOR SEARS, Chemistry Dept, Brookhaven National Laboratory, Upton, NY 11973; NEIL E. SHAFER-RAY, Homer L.
Dodge Department of Physics and Astronomy, University of Oklahoma, Norman, OK; LUKAS ALPHEI,
JENS-UWE GRABOW, Institut für Physikalische Chemie und Elektrochemie, Gottfried-Wilhelm-LeibnizUniverstät, 30167 Hannover, Germany.
TF11
PRECISE THEORETICAL STUDY OF SPECTROSCOPIC CONSTANTS IN DIATOMICS
10 min 4:20
L.V. SKRIPNIKOV, A.N. PETROV, A.V. TITOV, N.S. MOSYAGINa ,
a SPbU
Intermission
TF12
15 min 4:50
DETERMINATION OF THE BOLTZMANN CONSTANT BY MEANS OF DOPPLER-BROADENING THERMOMETRY ON WATER AT 1.39 µm.
L. MORETTI, A. CASTRILLO, E. FASCI, M.D. DE VIZIA, Dipartimento di Matematica e Fisica, Seconda
Università di Napoli, Caserta, Italy; G. GALZERANO, P. LAPORTA, Dipartimento di Fisica, Politecnico
di Milano and IFN-CNR, Milano, Italy; A. MERLONE, INRIM, Istituto Nazionale di Ricerca Metrologica,
Torino, Italy; and L. GIANFRANI, Dipartimento di Matematica e Fisica, Seconda Università di Napoli,
Caserta, Italy.
32
TF13
COMB-ASSISTED QCL DOPPLER-BROADENED THERMOMETRY IN NH3 SAMPLES
15 min 5:07
ANDREW A. MILLS, CHRISTIAN MOHR, JIE JIANG, IMRA America, Ann Arbor, MI; DAVIDE GATTI,
MARCO MARANGONI, Dipartimento di Fisica del Politecnico di Milano, Milano, Italy; MARIA
DOMENICA DE VIZIA, LIVIO GIANFRANI, Seconda Universita Di Napoli, Caserta, Italy; INGMAR
HARTL, Deutsches Eleketronen-Synchrotron, Hamburg, Germany; MARTIN FERMANN, IMRA America,
Ann Arbor, MI.
TF14
15 min 5:24
ULTRA-LOW PHASE NOISE, HIGH RESOLUTION SPECTROMETER USING COMB-ASSISTED QUANTUM CASCADE LASERS
MARCO MARANGONI, Dipartimento di Fisica del Politecnico di Milano, Milano, Italy; LIVIO GIANFRANI, Dipartimento di Matematica e Fisica della Seconda Universita Di Napoli, Caserta, Italy; INGMAR
Ann Arbor, MI.
TF15
NARROW OPPOSITE-PARITY LEVEL CROSSINGS IN A DIATOMIC RADICAL
10 min 5:41
S. B. CAHN, J. AMMON, Y. GUREVICH, E. ALTUNTAS, D. DEMILLE, Yale University, Dept. of Physics,
New Haven, CT, USA; R. PAOLINO, US Coast Guard Academy, New London, CT, USA; M. G. KOZLOV,
Petersburg Nuclear Physics Institute, Gatchina, Russia.
TF16
PHOTOELECTRON SPECTROSCOPY STUDIES OF URANIUM FLUORIDE
15 min 5:53
WEI-LI LI, TIAN JIAN, GARY V. LOPEZ, AND LAI-SHENG WANG , Brown University, Chemistry
Department, 324 Brook St, Providence, RI, 02912.
33
TG. MINI-SYMPOSIUM: THEORY AND SPECTROSCOPY
Chair: JOHN STANTON, The University of Texas at Austin, Austin, TX
TG01
INVITED TALK
DIABATIC VERSUS ADIABATIC CALCULATION OF TORSION-VIBRATION INTERACTIONS
30 min 1:30
JON T. HOUGEN, Sensor Science Division, NIST, Gaithersburg, MD 20899-8441, USA.
TG02
15 min 2:05
AB INITIO AND MODEL-HAMILTONIAN STUDY OF THE TORSIONAL VARIATION OF THE THREE CH
STRETCHING NORMAL MODES IN METHANOL
LI-HONG XU, RONALD M. LEES, Centre for Laser, Atomic and Molecular Sciences (CLAMS), Physics
Department, University of New Brunswick, 100 Tucker Park Road, Saint John, NB, Canada E2L 4L5; JON
T. HOUGEN, Sensor Sciences Division, National Institute of Standards and Technology, Gaithersburg, MD
20899-8441.
TG03
EXTENDING DIFFUSION MONTE CARLO TO INTERNAL COORDINATES
15 min 2:22
ANDREW S. PETIT and ANNE B. McCOY, Department of Chemistry and Biochemistry, The Ohio State
University, Columbus, OH 43210.
TG04
PATTERNS OF BROKEN PATTERNS
15 min 2:39
R. W. FIELD, G. B. PARK, P. B. CHANGALA, J. H. BARABAN, Department of Chemistry, Massachusetts
Institute of Technology, Cambridge, MA 02139, USA; J. F. STANTON, Institute for Theoretical Chemistry, Departments of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712;
A. J. MERER, Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan. Department of Chemistry, University of British Columbia, Vancouver, B.C., Canada V6T 1Z1.
TG05
ISOMERIZATION, PERTURBATIONS, CALCULATIONS AND THE S1 STATE OF C2 H2
15 min 2:56
J. H. BARABAN, P. B. CHANGALA, J. R. P. BERK, R. W. FIELD, Department of Chemistry, Massachusetts
TG06
15 min 3:13
REDUCED DIMENSION ROVIBRATIONAL VARIATIONAL CALCULATIONS OF THE S1 STATE OF C2 H2
P. B. CHANGALA, J. H. BARABAN, R. W. FIELD, Department of Chemistry, Massachusetts Institute of
Technology, Cambridge, MA 02139, USA; J. F. STANTON, Institute for Theoretical Chemistry, Department of
Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712; A. J. MERER, Institute
of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan;.
34
TG07
15 min 3:30
LEAST SQUARES FITTING OF PERTURBED VIBRATIONAL POLYADS NEAR THE ISOMERIZATION BARRIER
IN THE S1 STATE OF C2 H2
A. J. MERER, Department of Chemistry, University of British Columbia, Vancouver, B.C., Canada V6T 1Z1
AND Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan.; J. H. BARABAN,
P. B. CHANGALA, and R. W. FIELD, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
Intermission
TG08
15 min 4:00
COLLISIONAL LINE MIXING IN PARALLEL AND PERPENDICULAR BANDS OF LINEAR MOLECULES BY A
NON-MARKOVIAN APPROACH
JEANNA BULDYREVA, Institut UTINAM, UMR CNRS 6213, Université de Franche-Comté, 16 route de
Gray, 25030 Besançon cedex, France.
TG09
15 min 4:17
TUNNELING AND TUNNELING SWITCHING DYNAMICS IN PHENOL AND ORTHO-D-PHENOL: FTIR SPECTROSCOPY WITH SYNCHROTRON RADIATION AND THEORY
S. ALBERT, R PRENTNER, M. QUACK, PHYSICAL CHEMISTRY, ETH ZÜRICH, CH-8093 ZÜRICH,
SWITZERLAND; PH. LERCH, SWISS LIGHT SOURCE, PAUL-SCHERRER-INSTITUTE, CH-5232 VILLIGEN, SWITZERLAND.
TG10
15 min 4:34
ANHARMONIC VIBRATIONAL MØLLER-PLESSET PERTURBATION THEORIES USING THE DYSON EQUATION
MATTHEW R. HERMES and SO HIRATA, Department of Chemistry, University of Illinois at UrbanaChampaign, Urbana, IL 61801.
TG11
15 min 4:51
PERTURBATIVE CORRECTIONS TO THE CALCULATED TRANSITION FREQUENCY AND OSCILLATOR
STRENGTH OF THE HYDROGEN BONDED OH-OSCILLATOR IN THE DONOR WATER MOLECULE IN WATER
DIMER
KASPER MACKEPRANG, HENRIK G. KJAERGAARD, Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen ; TEEMU SALMI, LAURI HALONEN, Laboratory of
Physical Chemistry, Department of Chemistry, P.O. Box 55, A.I. Virtasen aukio 1, FI-00014, University of
Helsinki, Helsinki, Finland.
TG12
15 min 5:08
VIBRATIONAL CONSTANTS FOR TRIATOMIC MOLECULES FROM FOURTH-ORDER PERTURBATION THEORY
DEVIN A. MATTHEWS, JUSTIN Z. GONG, and JOHN F. STANTON, Department of Chemistry and Biochemistry, Institute for Theoretical Chemistry, The University of Texas at Austin, Austin, Texas 78712.
TG13
15 min 5:25
ROTATIONAL AND ROVIBRATIONAL CONSTANTS FOR TRIATOMIC MOLECULES FROM FOURTH-ORDER
PERTURBATION THEORY
35
TG14
15 min 5:42
APPLICATION OF FOURTH-ORDER VIBRATIONAL PERTURBATION THEORY TO SMALL MOLECULES
JUSTIN Z. GONG, DEVIN A. MATTHEWS, and JOHN F. STANTON, Department of Chemistry and Biochemistry, Institute for Theoretical Chemistry, The University of Texas at Austin, Austin, Texas 78712.
36
TH. MICROWAVE
Chair: GILLES ADANDE, University of Arizona, Tucson, AZ
TH01
15 min 1:30
THE SUB-MILLIMETER WAVE SPECTROSCOPY OF MONODUTERATED AMIDOGEN RADICAL (NHD)
YUTA MOTOKI, HIROYUKI OZEKI, Department of Environmental Science, Toho University, 2-2-1
Miyama, Funabashi, 274-8510, Japan; KAORI KOBAYASHI, Department of Physics, University of Toyama,
3190 Gofuku, Toyama, 930-8555, Japan.
TH02
FOURIER TRANSFORM MICROWAVE SPECTRUM OF N2 -(CH2 )2 O
15 min 1:47
YOSHIYUKI KAWASHIMA, Department of Applied Chemistry, Faculty of Engineering, Kanagawa Institute
of Technology, Atsugi, Kanagawa 243-0292, JAPAN; EIZI HIROTA, The Graduate University for Advanced
Studies, Hayama, Kanagawa 240-0193, JAPAN.
TH03
THE BROADBAND ROTATIONAL SPECTRUM AND GEOMETRY OF N2 · · · ICF3
15 min 2:04
N. R. WALKER, D. HIRD, School of Chemistry, Bedson Building, Newcastle University, Newcastle-uponTyne, NE1 7RU, U.K.; A. C. LEGON, School of Chemistry, University of Bristol, Bristol, BS8 1TS, U.K..
TH04
15 min 2:21
UNEXPECTED GENERATION AND OBSERVATION OF A T-SHAPED COMPLEX OF H2 C2 · · · AgCCH
N. R. WALKER, School of Chemistry, Bedson Building, Newcastle University, Newcastle-upon-Tyne, NE1
7RU, U.K.; S. L. STEPHENS, W. MIZUKAMI, D. P. TEW AND A. C. LEGON, School of Chemistry,
University of Bristol, Bristol, BS8 1TS, U.K..
TH05
15 min 2:38
STRUCTURES OF THE CAGE, PRISM, AND BOOK HEXAMER WATER CLUSTERS FROM MULTIPLE ISOTOPIC
SUBSTITUTION
SIMON LOBSIGER, CRISTOBAL PEREZ, DANIEL P. ZALESKI, NATHAN SEIFERT, BROOKS H.
ZBIGNIEW KISIEL, Institute of Physics, Polish Academy of Sciences, Al. Lotników 32/46, 02-668 Warszawa,
Poland; BERHANE TEMELSO, GEORGE C. SHIELDS, Dean’s Office, College of Arts and Sciences, and
Department of Chemistry, Bucknell University, Lewisburg, PA 17837.
TH06
15 min 2:55
CHARACTERIZATION OF LARGE WATER CLUSTERS BY BROADBAND ROTATIONAL SPECTROSCOPY
CRISTOBAL PEREZ, DANIEL P. ZALESKI, NATHAN A. SEIFERT, BROOKS H. PATE, Department of
Chemistry, University of Virginia, McCormick Rd., Charlottesville, VA 22904-4319; ZBIGNIEW KISIEL, Institute of Physics, Polish Academy of Sciences, Al. Lotników 32/46, 02-668 Warszawa, Poland; BERHANE
TEMELSO, GEORGE C. SHIELDS, Dean’s Office, College of Arts and Sciences, and Department of Chemistry, Bucknell University, Lewisburg, PA 17837; STEVEN T. SHIPMAN, IAN FINNERMAN, Division of
Natural Sciences, New College of Florida, Sarasota, FL 34243.
37
TH07
15 min 3:12
HYDROGEN BOND NETWORK ISOMERS OF THE WATER NONAMER AND DECAMER OBSERVED BY
BROADBAND ROTATIONAL SPECTROSCOPY
TEMELSO, GEORGE C. SHIELDS, Dean’s Office, College of Arts and Sciences, and Department of Chemistry, Bucknell University, Lewisburg, PA 17837.
TH08
15 min 3:29
STRUCTURES OF THE LOWEST ENERGY NONAMER AND DECAMER WATER CLUSTERS FROM CHIRPEDPULSE ROTATIONAL SPECTROSCOPY
CRISTOBAL PEREZ, BROOKS H. PATE, Department of Chemistry, University of Virginia, McCormick Rd.,
Charlottesville, VA 22904-4319; ZBIGNIEW KISIEL, Institute of Physics, Polish Academy of Sciences, Al.
Lotników 32/46, 02-668 Warszawa, Poland; BERHANE TEMELSO, GEORGE C. SHIELDS, Dean’s Office,
College of Arts and Sciences, and Department of Chemistry, Bucknell University, Lewisburg, PA 17837.
Intermission
TH09
15 min 4:00
MILLIMETER WAVE SPECTRA OF THE INTERNAL ROTATION EXCITED STATES OF (o)H2 -H2 O AND (o)H2 D2 O
K. HARADA, Y. IWASAKI, T. GIESEN, and K. TANAKA, Department of Chemistry, Faculty of Science,
Kyushu University, Hakozaki, Higashiku, Fukuoka, 812-8581 JAPAN.
TH10
15 min 4:17
THE PERFORMANCE OF THE THIRD GENERATION OF CP-FTMW SPECTROMETERS ILLUSTRATED BY THE
ANALYSIS OF THE WATER HEPTAMER STRUCTURE
CRISTOBAL PEREZ, DANIEL P. ZALESKI, NATHAN A. SEIFERT, SIMON LOBSIGER, BROOKS H.
Department of Chemistry, Bucknell University, Lewisburg, PA 17837; STEVEN T. SHIPMAN, Division of
Natural Sciences, New College of Florida, Sarasota, FL 34243; DAVID W. PRATT, Department of Chemistry,
The University of Vermont, Cook Physical Sciences Building, 82 University Place, Burlington, VT 05405.
TH11
THE CYTOSINE WATER COMPLEX
10 min 4:34
A. M. DALY, S. MATA, C. BERMUDEZ, M. BERDAKIN, I. PENA, C. CABEZAS, J. L. ALONSO, Grupo
de Espectroscopía Molecular (GEM), Edificio Quifima, Laboratorios de Espectroscopía y Bioespectroscopía,
Parque Científico, Universidad de Valladolid, 47011 Valladolid, Spain.
TH12
EXPERIMENTAL EVIDENCE OF LONE PAIRS - π SYSTEM INTERACTION:
TRUM OF CHLOROTRIFLUOROETHYLENE - WATER COMPLEX
10 min 4:46
THE ROTATIONAL SPEC-
L. EVANGELISTI, Q. GOU, G. FENG and W. CAMINATI, Dipartimento di Chimica "G. Ciamician"
dell’Universitá, Via Selmi 2, I-40126 Bologna, Italy.
38
TH13
15 min 4:58
MICROWAVE SPECTRA AND STRUCTURE OF H2 –CuF: OVERVIEW OF THE COMPLEXES OF HYDROGEN
WITH METAL-CONTAINING DIATOMICS
G. S. GRUBBS II, DANIEL J. FROHMAN, Department of Chemistry, Wesleyan University, 52 Lawn Avenue,
Middletown, CT, 06459-0180, USA; ZHENHONG YU, Aerodyne Research, Inc. 45 Manning Road, Billerica, MA 01821; STEWART E. NOVICK, Department of Chemistry, Wesleyan University, 52 Lawn Avenue,
Middletown, CT, 06459-0180, USA (email to SEN: [email protected]).
TH14
15 min 5:15
EFFECTS OF A REMOTE BINDING PARTNER ON THE ELECTRIC FIELD AND ELECTRIC FIELD GRADIENT AT
AN ATOM IN A WEAKLY BOUND TRIMER: MICROWAVE SPECTROSCOPY AND QUANTUM MECHANICAL
COMPUTATIONS ON Kr-SO3 AND Kr-SO3 -CO
REBECCA B. MACKENZIE, BROOKE A. TIMP, KENNETH R. LEOPOLD, Department of Chemistry, University of Minnesota, 207 Pleasant St., SE, Minneapolis, MN 55455; YIRONG MO, Department of Chemistry,
Western Michigan University, Kalamazoo, MI 49008.
TH15
15 min 5:32
MICROWAVE SPECTRUM AND STRUCTURE OF THE 2,6-DIFLUOROPYRIDINE-CO2 COMPLEX
CHRISTOPHER T. DEWBERRY, Department of Chemistry, University of Minnesota, 207 Pleasant St., SE,
Minneapolis, MN 55455; JESSICA L. MUELLER, MARK D. MARSHALL, HELEN O. LEUNG, Department of Chemistry, Amherst College, P.O. Box 5000, Amherst, MA 01002-5000; KENNETH R. LEOPOLD,
Department of Chemistry, University of Minnesota, 207 Pleasant St., SE, Minneapolis, MN 55455.
TH16
15 min 5:49
OBSERVATION OF A MODERATE STRENGTH INTERACTION OF HYDROGEN WITH A COINAGE METAL
HALIDE: THE ROTATIONAL SPECTRUM AND STRUCTURE OF THE p-H2 -CuCl AND o-H2 -CuCl COMPLEXES
HERBERT M. PICKETT, DANIEL A. OBENCHAIN, G. S. GRUBBS II, and STEWART E. NOVICK, Department of Chemistry, Wesleyan University, 52 Lawn Avenue, Middletown, CT, 06459-0180, USA.
39
TI. ASTRONOMICAL SPECIES AND PROCESSES
Chair: ERIC HERBST, University of Virginia, Charlottesville, VA
TI01
15 min 1:30
LARGE PICTURE OF THE GALACTIC CENTER STUDIED BY H+
3 : HIGH IONIZATION RATE, PREVAILING
WARM AND DIFFUSE GAS, AND NON-ROTATING EXPANDING MOLECULAR RING
TAKESHI OKA, Department of Astronomy and Astrophysics, Department of Chemistry, the Enrico Fermi
Institute, University of Chicago, Chicago, IL 60637; THOMAS R. GEBALLE, Gemini Observatory, Hilo,
HI 96720; NICK INDRIOLO, Department of Physics and Astronomy, Johns Hopkins University, Baltimore,
MD 21218.
TI02
EXPLORING SHOCK CHEMISTRY IN ORION-KL WITH MID-J MOLECULAR TRANSITIONS
15 min 1:47
JULIE K. ANDERSON and LUCY M. ZIURYS, Department of Chemistry and Biochemistry, The University
of Arizona, Tucson, AZ 85719.
TI03
15 min 2:04
FORMATION OF CH : SHOCK CHEMISTRY IN NGC 7027
+
JULIE K. ANDERSON, Department of Chemistry and Biochemistry, The University of Arizona, Tucson, AZ
85719; LUCY M. ZIURYS, Department of Chemistry and Biochemistry, The University of Arizona, Tucson,
AZ 85719; FABRICE HERPIN, LAB-OASU, France.
TI04
15 min 2:21
WARM, DENSE GAS NEAR THE MASSIVE PROTOSTAR AFGL 2136 IRS 1 AS REVEALED BY ABSORPTION
FROM THE ν1 , ν2 , AND ν3 BANDS OF WATER
NICK INDRIOLO, DAVID A. NEUFELD, Department of Physics & Astronomy, Johns Hopkins University,
Baltimore, MD 21218; ANDREAS SEIFAHRT, Department of Astronomy and Astrophysics, University of
Chicago, Chicago, IL 60637; MATT J. RICHTER, Department of Physics, University of California Davis,
Davis, CA 95616.
TI05
15 min 2:38
NEW RESULTS FROM A SPECTRAL-LINE SURVEY OF Sgr B2(N): INSIGHT INTO GAS-PHASE PROCESSES
D. T. HALFEN and L. M. ZIURYS, Department of Chemistry, Department of Astronomy, and Steward Observatory, University of Arizona, Tucson, AZ 85721.
TI06
15 min 2:55
CSO BROADBAND MOLECULAR LINE SURVEYS I: BENCHMARKING GOBASIC ANALYSIS SOFTWARE
MARY L. RADHUBER, JAMES L. SANDERS III, JACOB C. LAAS, BRIAN M. HAYS, SUSANNA L.
WIDICUS WEAVER, Department of Chemistry, Emory University, Atlanta, GA 30322; DAREK C. LIS,
Division of Physics, Mathematics, and Astronomy, California Institute of Technology, Pasadena, CA 91125.
40
TI07
15 min 3:12
CSO BROADBAND MOLECULAR LINE SURVEYS II: INTIAL CORRELATION ANALYSIS RESULTS FOR COMPLEX ORGANIC MOLECULES
JAMES L. SANDERS III, MARY L. RADHUBER, JACOB C. LAAS, BRIAN M. HAYS, DAREK C. LIS
and SUSANNA L. WIDICUS WEAVER, Emory University, Department of Chemistry, Atlanta, Georgia
30322.
TI08
DETECTION AND FORMATION OF INTERSTELLAR c-C3 D2
15 min 3:29
SILVIA SPEZZANO, SANDRA BRÜNKEN, PETER SCHILKE, I. Physikalisches Institut, Universität zu
Köln, Zülpicher Str. 77, 50937 Köln, Germany; KARL M. MENTEN, Max-Planck-Institut für Radioastronomie, Auf dem Hügel 69, 53121 Bonn, Germany; PAOLA CASELLI, School of Physics and Astronomy,
University of Leeds, Leeds LS2 9JT, UK; MICHAEL C. McCARTHY, Harvard-Smithsonian Center for Astrophysics, 60 Garden St., Cambridge, MA 02138, and School of Engineering & Applied Sciences, Harvard
University, 29 Oxford St., Cambridge, MA 02138; LUCA BIZZOCCHI, Centro de Astronomia e Astrofísica,
Observatório Astronómico de Lisboa, Tapada da Ajuda, 1349-018 Lisboa, Portugal; SANDRA TREVINO,
IRAM, 18012, Granada, Spain; YURI AIKAWA, Department of Earth and Planetary Sciences, Kobe University, Kobe 657-8501, Japan; and STEPHAN SCHLEMMER, I. Physikalisches Institut, Universität zu Köln,
Zülpicher Str. 77, 50937 Köln, Germany.
Intermission
TI09
15 min 4:00
TERAHERTZ TIME DOMAIN SPECTROSCOPY OF COMPLEX ORGANIC MOLECULES IN ASTROPHYSICALLY
RELEVANT ICES
BRETT A. McGUIRE, Division of Chemistry and Chemical Engineering, California Institute of Technology,
Pasadena, CA 91125; SERGIO IOPPOLO, Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125; MARCO A. ALLODI, MATTHEW J. KELLEY, Division of
TI10
15 min 4:17
THE ANALYSIS OF ACETONITRILE (CH3 CN) USING 3-D SUBMILLIMETER SPECTROSCOPY
JAMES P. MCMILLAN, SARAH M. FORTMAN, CHRISTOPHER F. NEESE, FRANK C. DE LUCIA, Department of Physics, The Ohio State University, Columbus, OH 43210.
TI11
15 min 4:34
THE COMPLETE, TEMPERATURE RESOLVED EXPERIMENTAL SPECTRUM OF METHANOL BETWEEN 560
AND 654 GHZ
SARAH M. FORTMAN, CHRISTOPHER F. NEESE, and FRANK C. DE LUCIA, Department of Physics,
The Ohio State University, 191 W. Woodruff Ave., Columbus, OH 43210.
TI12
SPECTROSCOPY OF ISOCYANIDES AND THEIR SEARCH IN INTERSTELLAR MEDIUM
15 min 4:51
L. MARGULÈS, R. A. MOTIYENKO, Laboratoire PhLAM, CNRS UMR 8523, Université de Lille 1, 59655
Villeneuve d’Ascq Cedex, France; B. TERCERO, J. CERNICHARO, Centro de Astrobiología (CSIC-INTA).
Laboratory of Molecular Astrophysics. Department of Astrophysics. Ctra de Ajalvir,Km 4, 28850 Torrejón
de Ardoz, Madrid, Spain; and J.-C. GUILLEMIN, Sciences Chimiques de Rennes, UMR 6226 CNRS-ENSCR,
Avenue du Général Leclerc, CS 50837, 35708 Rennes Cedex 7, France.
41
TI13
15 min 5:08
SUBMILLIMETERWAVE SPECTROSCOPY OF HIGHLY ASTROPHYSICAL INTEREST MOLECULE: HYDROXYACETONITRILE
Villeneuve d’Ascq Cedex, France; and J.-C. GUILLEMIN, Sciences Chimiques de Rennes, UMR 6226 CNRSENSCR, Avenue du Général Leclerc, CS 50837, 35708 Rennes Cedex 7, France.
TI14
15 min 5:25
LABORATORY MEASUREMENTS AND ASTRONOMICAL OBSERVATIONS OF H2 NCO
+
HARSHAL GUPTA, Morrisroe Astrocience Laboratory, California Institute of Technology, Pasadena, CA
91125; CARL A. GOTTLIEB AND MICHAEL C. MCCARTHY, Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138.
TI15
15 min 5:42
MILLIMETER AND SUBMILLIMETER WAVE SPECTRA OF THE HCOO13 CH3 ISOTOPOLOG OF METHYLFORMATE IN THE GROUND STATE AND IN THE FIRST EXCITED TORSIONAL STATE.
I. HAYKAL, L. MARGULÈS, T. R. HUET, R. A. MOTIYENKO, Laboratoire PhLAM, UMR8523 CNRSUniversité Lille 1, F-59655 Villeneuve d’Ascq Cedex, France; M. CARVAJAL, Unidad Asociada IEM-CSICDpto. de Física Aplicada, Universidad de Huelva, Spain; I. KLEINER, LISA, CNRS et Université Paris Est
et Paris Diderot, 61 av. Général de Gaulle, 94010, Créteil, France; J. C. GUILLEMIN, ENS de Chimie de
Rennes -CNRS -35700 Rennes, France; B. TERCERO, J. CERNICHARO, Centro de Astrobiología (CSICINTA). Ctra de Ajalvir, Km 4, 28850 Torrejón de Ardoz, Madrid, Spain.
42
TJ. INFRARED/RAMAN
Chair: BRIAN BRUMFIELD, Princeton University, Princeton, NJ
TJ01
15 min 1:30
SUB-DOPPLER RESOLUTION SPECTROSCOPY OF THE FUNDAMENTAL BAND OF HCl WITH AN OPTICAL
FREQUENCY COMB
K. IWAKUNI and M. ABE and H. SASADA, Department of Physics, Faculty of Science and Technology, Keio
University, 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
TJ02
15 min 1:47
ABSOLUTE MEASUREMENTS OF NEAR-INFRARED CO2 TRANSITION FREQUENCIES AT THE kHz-LEVEL
DAVID A. LONG, GAR-WING TRUONG, JOSEPH T. HODGES, Material Measurement Laboratory, National Institute of Standards and Technology, 100 Bureau Drive, Gaithersburg, MD 20899, USA; and
CHARLES E. MILLER, Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive,
Pasadena, CA 91109, USA.
TJ03
15 min 2:04
ACCURATE DETERMINATION OF ROTATIONAL ENERGY LEVELS IN THE GROUND STATE OF 12 CH4
M. ABE, K. IWAKUNI, S. OKUBO and H. SASADA, Department of Physics, Faculty of Science and Technology, Keio University, Yokohama, Japan.
TJ04
10 min 2:21
IR/THZ DOUBLE RESONANCE SPECTROSCOPY IN THE PRESSURE BROADENED REGIME: A PATH TOWARDS ATMOSPHERIC GAS SENSING
S. SREE HARSHA , Aegis Technologies, 410 Jan Davis Drive, Huntsville, Alabama 35806; DANE J.
PHILLIPS, IERUS Technologies, 2904 Westcorp Blvd, Ste 210, Huntsville, AL 35805; FRANK C. DE LUCIA, Department of Physics, 191 Woodruff Ave., Ohio State University, Columbus, OH 43210 ; HENRY O.
EVERITT , Army Aviation and Missile RDE Center, Redstone Arsenal, AL 35898.
TJ05
15 min 2:33
DETECTION OF NO AND S-NITROSOCOMPOUNDS USING MID-IR CAVITY RING-DOWN SPECTROSCOPY
VITALI STSIAPURA, VINCENT K. SHUALI, ANGELA ZIEGLER, KEVIN K. LEHMANN, Chemistry
Department, University of Virginia, Charlottesville, VA 22904; and BENJAMIN M. GASTON, Case Western
Reserve University, Cleveland, Ohio 44106.
TJ06
15 min 2:50
DIFFERENTIAL OPTICAL DISPERSION SPECTROSCOPY FOR COMPARATIVE MOLECULAR QUANTIFICATION
MICHAL NIKODEM, BRIAN BRUMFIELD, GERARD WYSOCKI, Department of Electrical Engineering,
Princeton University, Princeton, NJ, 08544, USA.
Intermission
43
TJ07
STUDY OF UTILIZATION OF AUTOMOTIVE DIESEL GLOW PLUG AS AN IR SOURCE
5 min 3:30
ALLEN R. WHITE, Department of Mechanical Engineering, Rose-Hulman Institute of Technology, 5500
Wabash Ave., Terre Haute, IN 47803.
TJ08
FTIR STUDY OF COMUSTION SPECIES IN SEVERAL REGIONS OF A CANDLE FLAME
10 min 3:37
TJ09
15 min 3:49
SPONTANEOUS RAMAN SCATTERING MEASUREMENTS OF NITROGEN VIBRATIONAL DISTRIBUTION
FUNCTION IN NANOSECOND PULSED DISCHARGE
A. ROETTGEN, I.V. ADAMOVICH, W.R. LEMPERT, Machael A. Chaszeyka Nonequilibrium Thermodynamics Laboratory, Dept. of Mechanical and Aerospace Engineering, The Ohio State University, Columbus,
OH 43210.
TJ10
15 min 4:06
STIMULATED INFRARED EMISSION OF C2 H2 NEAR 3000 cm
−1
WITH CONTINUOUS-WAVE LASERS
MIKAEL SILTANEN, MARKUS METSÄLÄ, MARKKU VAINIO, and LAURI HALONEN, Department of
Chemistry, University of Helsinki, P.O. Box 55, FIN-00014 Helsinki, Finland.
TJ11
15 min 4:23
CONTINUOUS WAVE STIMULATED RAMAN SPECTROSCOPY INSIDE A HOLLOW CORE PHOTONIC CRYSTAL FIBER
JOSÉ L. DOMÉNECH and MAITE CUETO, Instituto de Estructura de la Materia (IEM-CSIC), Serrano 123,
E-28006 Madrid, Spain. (email to J.L.D.: [email protected]).
TJ12
15 min 4:40
DEVELOPMENT OF AN EXTERNAL CAVITY QUANTUM CASCADE LASER SPECTROMETER FOR HIGHRESOLUTION SPECTROSCOPY OF MOLECULAR IONS
JACOB T. STEWART, BRADLEY M. GIBSON, Department of Chemistry, University of Illinois at UrbanaChampaign, Urbana, IL 61801; BENJAMIN J. McCALL, Departments of Chemistry and Astronomy, University of Illinois at Urbana-Champaign, Urbana, IL 61801.
TJ13
15 min 4:57
FELION: A CRYOGENIC ION TRAP APPARATUS FOR SPECTROSCOPIC STUDIES WITH FELIX
S. BRÜNKEN, L. KLUGE, S. FANGHÄNEL, A. POTAPOV, O. ASVANY, and S. SCHLEMMER,
I. Physikalisches Institut, Universität zu Köln, 50937 Köln, Germany; J. OOMENS, B. REDLICH, Radboud
University Nijmegen, Institute for Molecules and Materials, FELIX Facility, 6525 ED Nijmegen, Netherlands;
A. STOFFELS, I. Physikalisches Institut, Universität zu Köln, 50937 Köln, Germany, and Radboud University
Nijmegen, Institute for Molecules and Materials, FELIX Facility, 6525 ED Nijmegen, Netherlands.
TJ14
15 min 5:14
DEVELOPMENT OF A SHEATH-FLOW SUPERCRITICAL FLUID EXPANSION SOURCE FOR VAPORIZATION
OF NONVOLATILES AT MODERATE TEMPERATURES
BRADLEY M. GIBSON and JACOB T. STEWART, Department of Chemistry, University of Illinois at
Urbana-Champaign, Urbana, IL 61801; BENJAMIN J. McCALL, Departments of Chemistry and Astronomy, University of Illinois at Urbana-Champaign, Urbana, IL 61801.
44
TJ15
15 min 5:31
A NEW FAR-IR (THz) AND IR SPECTROMETER FOR THE STUDY OF ASTROCHEMICAL ICES
MARCO A. ALLODI, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125; SERGIO IOPPOLO, Division of Geology and Planetary Science, California Institute of Technology, Pasadena, CA 91125; BRETT A. McGUIRE, MATTHEW J. KELLEY, Division of
Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125; and GEOFFREY A. BLAKE, Division of Geology and Planetary Science, and Division of Chemistry and Chemical
Engineering, California Institute of Technology, Pasadena, CA 91125.
TJ16
15 min 5:48
DEVELOPMENT AND APPLICATION OF A HIGHER RESOLUTION TERAHERTZ TIME-DOMAIN SPECTROMETER
DANIEL B. HOLLAND, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125 (email to D.B.H.: [email protected]); GEOFFREY A. BLAKE, Division of
Geological and Planetary Sciences, Division of Chemistry and Chemical Engineering, California Institute of
Technology, Pasadena, CA 91125.
45
TK. ELECTRONIC
Chair: SCOTT REID, Marquette University, Milwaukee, WI
TK01
15 min 1:30
THE CHARACTER OF THE LONG-LIVED STATE FORMED FROM S1 OF PHENYLACETYLENE
PHILIP M. JOHNSON AND TREVOR J. SEARSa , Department of Chemistry, Stony Brook University, Stony
Brook, New York 11794.
a also:
TK02
TWO-PROTON PHOTOTAUTOMERIZATION DYNAMICS OF 7-AZAINDOLE COMPLEXES
15 min 1:47
T. CHAKRABORTY, M. MUKHERJEE and S. KARMAKAR, Department of Physical Chemistry, Indian
Association for the cultivation of science, Calcutta 700032, India.E-mail: [email protected].
TK03
15 min 2:04
STRUCTURE DETERMINATION AND EXCITED STATE PROTON TRANSFER REACTION OF 1-NAPHTHOLAMMONIA CLUSTERS IN THE S1 STATE STUDIED BY UV-IR-UV MID-IR SPECTROSCOPY
SHUNPEI YOSHIKAWA, MITSUHIKO MIYAZAKI, WEILER MARTIN, Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8503 Japan; HARUKI
ISHIKAWA, Depertment of Chemistry, School of Science, Kitasato University, Minami-ku, Sagamihara
252-0373, Japan; MASAAKI FUJII, Chemical Resources Laboratory, Tokyo Institute of Technology, 4259
Nagatsuta-cho, Midori-ku, Yokohama 226-8503 Japan.
TK04
LASER DESORPTION SUPERSONIC JET SPECTROSCOPY OF HYDRATED TYROSINE
15 min 2:21
HIKARI OBA, YOKO SHIMOZONO, SHUN-ICHI ISHIUCHI, MASAAKI FUJII, Chemical Resources Lab.
Tokyo Tech. 4259 Nagatsuta-cho, Midoriku, Yokohama, 226-8503, Japan; PIERRE CARCABAL, ISMO.
Université Paris Sud XI Bâtiment 210, 91405, Orsay, Paris, France.
TK05
15 min 2:38
EXCITED-STATE DYNAMICS IN FOLIC ACID AND 6-CARBOXYPTERIN UPON UVA EXCITATION
HUIJUAN HUANG, R. AARON VOGT and CARLOS E. CRESPO-HERNÁNDEZ, Department of Chemistry and Center for Chemical Dynamics, Case Western Reserve University, Cleveland, Ohio 44106.
TK06
15 min 2:55
RESONANCE ENHANCED MULTI-PHOTON IONIZATION (REMPI) AND DOUBLE RESONANCE (UV-UV AND
IR-UV) SPECTROSCOPIC INVESTIGATION ISOCYTOSINE
SEUNG JUN LEE, AHREUM MIN, AHREUM AHN, CHEOL JOO MOON, MYONG YONG CHOI, Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju
660-701, Korea; SHUN-ICHI ISHIUCHI, MITSUHIKO MIYAZAKI, MASAAKI FUJII, Tokyo Institute of
Technology, Chemical Resources Laboratory, Japan.
46
TK07
15 min 3:12
RESONANCE ENHANCED MULTI-PHOTON IONIZATION AND UV-UV HOLE-BURNING SPECTROSCOPIC
STUDIES OF JET-COOLED ACETANILIDE DERIVATIVES
CEOL JOO MOON and AHREUM MIN, AHREUM AHN, SEUNG JUN LEE, MYONG YONG CHOI, Department of Chemistry (BK21), Gyeongsang National University, 501 Jinju Daero, Jinju 600-701, South Korea; SEONG KEUN KIM, Department of Chemistry and Biophysics & Biophysical Chemistry (WCU) Seoul
National University, Seoul 151-747, South Korea.
TK08
15 min 3:29
TAILOR MADE SYNTHESIS OF T-SHAPED AND π-STACKED DIMERS IN THE GAS PHASE: CONCEPT FOR
EFFICIENT DRUG DESIGN AND MATERIAL SYNTHESIS
SUMIT KUMAR and ALOKE DAS, Indian Institute of Science Education and Research (IISER), 900 NCL
Innovation Park, Dr. Homi Bhabha Road, Pune-411008, Maharashtra, India..
Intermission
TK09
15 min 4:00
ROTATIONALLY RESOLVED HIGH-RESOLUTION LASER SPECTROSCOPY OF THE S1 ← S0 TRANSITION OF
NAPHTHALENE AND Cl-NAPHTHALENE
SHUNJI KASAHARA, RYO YAMAMOTO, KOHEI TADA, Molecular Photoscience Research Center, Kobe
University, Kobe 657-8501, Japan.
TK10
VIBRONIC SPECTROSCOPY OF 4-ISOCYANOBENZONITRILE
15 min 4:17
JOSEPH A. KORN, DEEPALI N. MEHTA-HURT and TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN,47907.
TK11
15 min 4:34
STEPWISE SOLVATION EFFECTS ON THE EXCITED STATES OF A WEAKLY COUPLED BICHROMOPHORE:
1,2-DIPHENOXYETHANE-(H2O)N (N=2-4) CLUSTERS
PATRICK S. WALSH, EVAN G. BUCHANAN, JOSEPH R. GORD and TIMOTHY S. ZWIER, Department
of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN 47907.
TK12
15 min 4:51
PLANT SUNSCREENS IN NATURE: UV AND IR SPECTROSCOPY OF SINAPATE DERIVATIVES
JACOB C. DEAN, PATRICK S. WALSH, and TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN 47907; FLORENT ALLAIS, AgroParisTech, Paris, France.
TK13
15 min 5:08
FLUORESCENCE EXCITATION SPECTRA OF PHOTO-FRAGMENTED NITROBENZENE USING A PICOSECOND LASER: POTENTIAL EVIDENCE FOR NO PRODUCED BY TWO DISTINCT CHANNELS.
47
TK14
SPECTROSCOPIC CHARACTERIZATION OF A NATURAL PRODUCT: ANETHOLE
15 min 5:25
VICTORIA P. BARBER AND JOSH J. NEWBY, Department of Chemistry and Biochemistry, Swarthmore
College, Swarthmore, PA 19081.
48
WA. PLENARY
WEDNESDAY, JUNE 19, 2013 – 8:30 AM
Chair: ANNE MCCOY, The Ohio State University, Columbus, OH
WA01
40 min 8:30
CHARGE TRANSFER REACTIONS INDUCE BORN-OPPENHEIMER BREAKDOWN IN SURFACE CHEMISTRY:
APPLICATIONS OF DOUBLE RESONANCE SPECTROSCOPY IN MOLECULE-SURFACE SCATTERING
ALEC M. WODTKE, Georg-August University of Göttingen and the Max-Planck-Institute for Biophysical
Chemistry, Göttingen, Germany.
WA02
40 min 9:15
ULTRA SENSITIVE CAVITY RING DOWN SPECTROSCOPY OF MAJOR ATMOSPHERIC SPECIES BETWEEN
1.20 AND 1.71 µm
A. CAMPARGUE, S. KASSI, and D. MONDELAIN, Université Grenoble 1/CNRS, UMR5588 LIPhy, Grenoble, F-38041, France.
Intermission
WA03
INFRARED STUDIES OF METAL CATION-DIHYDROGEN COMPLEXES
40 min
10:20
40 min
11:05
EVAN BIESKE, School of Chemistry, University of Melbourne, 3010, Australia.
WA04
SPECTROSCOPIC ENGINEERING IN THE SUBMILLIMETER
FRANK C. DE LUCIA, DEPARTMENT OF PHYSICS, OHIO STATE UNIVERSITY, COLUMBUS, OH
43210.
49
WF. ASTRONOMICAL SPECIES AND PROCESSES
WEDNESDAY, JUNE 19, 2013 – 1:30 PM
Chair: SANDRA BRUENKEN, University of Cologne, Koeln, Germany
WF01
15 min 1:30
RADIATIVE LIFETIME FOR NUCLEAR SPIN CONVERSION OF WATER-ION, H2 O
+
KEIICHI TANAKA, Department of Applied Chemistry, National Chiao Tung University, Hsinchu, 30010,
TAIWAN and Department of Chemistry, Faculty of Sciences, Kyushu University, Fukuoka, 812-8581 JAPAN;
KENSUKE HARADA, Department of Chemistry, Faculty of Sciences, Kyushu University, Fukuoka, 8128581 JAPAN; TAKESHI OKA, Department of Astronomy and Astrophysics and Department of Chemistry, the
Enrico Fermi Institute, the University of Chicago, Chicago, Illinois, 60637, USA.
WF02
15 min 1:47
A MM/SUBMM WAVE SPECTROMETER TO QUANTIFY ASTROCHEMICAL REACTION RATES
JACOB C. LAAS and SUSANNA L. WIDICUS WEAVER, Department of Chemistry, Emory University, Atlanta, GA 30322.
WF03
15 min 2:04
UNIFIED MICROSCOPIC-MACROSCOPIC MONTE CARLO SIMULATION OF ICE FORMATION ON INTERSTELLAR GRAINS
QIANG CHANG, Department of Chemistry, University of Virginia, Charlottesville, Virginia, USA; ERIC
HERBST, Department of Chemistry, Physics and Astronomy, University of Virginia, Charlottesville, Virginia,
USA.
WF04
15 min 2:21
THE LOW-TEMPERATURE NUCLEAR SPIN EQUILIBRIUM OF H+
3 IN COLLISIONS WITH H2
FLORIAN GRUSSIE, MAX H. BERG, ANDREAS WOLF, and HOLGER KRECKEL, Max-Planck-Institut
für Kernphysik, 69117 Heidelberg, Germany; KYLE N. CRABTREEa and BENJAMIN J. McCALL, Department of Chemistry, University of Illinois, Urbana, IL, 61801; SABRINA GÄRTNER and STEPHAN
SCHLEMMER, I. Physikalisches Institut, Universität zu Köln, 50937 Köln, Germany.
a Present
address: Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, 02138
WF05
15 min 2:38
MOLECULAR HYDROGEN FORMATION : EFFECT OF DUST GRAIN TEMPERATURE FLUCTUATIONS
EMERIC BRON, JACQUES LE BOURLOT and FRANCK LE PETIT, LUTH - Observatoire de Paris, CNRS
UMR 8102, Université Paris Diderot. e-mail : [email protected].
WF06
15 min 2:55
REVISED TERM VALUES FOR THE A − X (v = 0-9, v = 0) BANDS IN
SPECTRA ACQUIRED AT THE SOLEIL SYNCHROTRON
′
′′
13
C O FROM HIGH-RESOLUTION
16
L. GAVILAN, J. L. LEMAIRE, M. EIDELSBERG, Observatoire de Paris, Paris, France; S. R. FEDERMAN,
Department of Physics and Astronomy, University of Toledo, Toledo, OH 43606; G. STARK, A. N. HEAYS,
Department of Physics, Wellesley College, Wellesley, MA 02481; J. H. FILLION, Université PVI UMPC,
Paris, France; J. R. LYONS, IGPP, University of Califormia, Los Angeles, CA 90095; N. DE OLIVEIRA,
Synchrotron SOLEIL, Saint Aubin, France.
50
Intermission
WF07
15 min 3:30
PHOTOIONIZATION AND RECOMBINATION OF Ne IV AND EXCITATION OF NeV IN NEBULAR PLASMAS
SULTANA N. NAHAR, ETHAN PALAY, ANIL K. PRADHAN, Department of Astronomy, The Ohio State
WF08
15 min 3:47
THE ‘4050 Å GROUP’ OF THE Ã1 Πu - X̃1 Σ+
g TRANSITION SYSTEM OF C3
D. ZHAO, H. LINNARTZ, Sackler Laboratory for Astrophysics, Leiden Observatory, University of Leiden,
P.O. Box 9513, NL-2300 RA Leiden, the Netherlands; M. A. HADDAD, W. UBACHS, LaserLaB, VU University Amsterdam, De Boelelaan 1081, NL-1081 HV, Amsterdam, The Netherlands; M. R. SCHMIDT, Department of Astrophysics, N. Copernicus Astronomical Center, ul. Rabiańska 8, 87-100 Toruń, Poland;
J. KRELOWSKI, Centre for Astronomy, Nicolaus Copernicus University, Gagarina 11, 87-100 Toruń, Poland;
G. A. GALAZUTDINOV, Instituto de Astronomia, Universidad Catolica del Norte, Av. Angamos 0610,
Antofagasta, Chile.
WF09
15 min 4:04
A NEW METHODOLOGY FOR THE DETECTION OF LOW-ABUNDANCE SPECIES IN THE ISM:
DETECTION OF INTERSTELLAR CARBODIIMIDE (HNCNH)
Pasadena, CA 91125; RYAN A. LOOMIS, Department of Chemistry, University of Virginia, Charlottesville,
VA 22904; CAMERON M. CHARNESS, JOANNA F. CORBY, Department of Astronomy, University of Virginia, Charlottesville, VA 22904; GEOFFREY A. BLAKE, Division of Chemistry and Chemical Engineering
and Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125;
JAN M. HOLLIS, NASA Goddard Space Flight Center, Greenbelt, MD 20771; FRANK J. LOVAS, National
Institute of Standards and Technology, Gaithersburg, MD 20899; PHILIP R. JEWELL, and ANTHONY J.
REMIJAN, National Radio Astronomy Observatory, Charlottesville, VA 22903.
WF10
INDIRECT ROTATIONAL SPECTROSCOPY OF HCO
15 min 4:21
+
ADAM J. PERRY, JAMES N. HODGES, BRIAN M. SILLER, Department of Chemistry, University of Illinois, Urbana, IL 61801; BENJAMIN J. MCCALL, Departments of Chemistry, Astronomy, and Physics, University of Illinois, Urbana, IL 61801.
WF11
15 min 4:38
SLIT-JET DISCHARGE STUDIES OF POLYACETYLENIC MOLECULES: SYNTHESIS AND HIGH RESOLUTION
INFRARED SPECTROSCOPY OF DIACETYLENE
CHIH-HSUAN CHANG, MELANIE A. ROBERTS, and DAVID J. NESBITT, JILA, National Institute of
WF12
15 min 4:55
SUB-DOPPLER SLIT JET DISCHARGE SPECTROSCOPY OF JET COOLED POLYACETYLENES: THE ANTISYMMETRIC CH STRETCH MODE OF TRIACETYLENE
51
WF13
A LINE LIST FOR HYDROGEN SULFIDE
15 min 5:12
ALA’A A. A. AZZAM, SERGEI N. YURCHENKO, JONATHAN TENNYSON, Department of Physics and
Astronomy, University College London, London, WC1E 6BT, UK.
WF14
ANALYSIS OF THE SUB-MILLIMETER ROTATIONAL SPECTRUM OF UREA
15 min 5:29
JESSICA R. THOMAS, ALYSSA M. FOSNIGHT, IVAN R. MEDVEDEV, Department of Physics, Wright
State University, 3640 Colonel Glenn Highway, Dayton, OH 45435, USA.
WF15
10 min 5:46
THE ROTATIONAL SPECTRUM OF COMPLEX ORGANIC MOLECULES: 2(N)-METHYLAMINOETHANOL
S. MELANDRI, A. MARIS and C. CALABRESE, Dipartimento di Chimica Ciamician, Università di
Bologna, via Selmi 2,40126 Bologna, Italy.
52
WG. MINI-SYMPOSIUM: THEORY AND SPECTROSCOPY
Chair: G. BARNEY ELLISON, University of Colorado, Boulder, CO
WG01
INVITED TALK
30 min 1:30
COMBINING THEORY AND EXPERIMENT TO COMPUTE HIGHLY ACCURATE LINE LISTS FOR STABLE
MOLECULES, AND PURELY AB INITIO THEORY TO COMPUTE ACCURATE ROTATIONAL AND ROVIBRATIONAL LINE LISTS FOR TRANSIENT MOLECULES
TIMOTHY J. LEE, XINCHUAN HUANG, RYAN C. FORTENBERRY, Space Science and Astrobiology Division, NASA Ames Research Center; DAVID W. SCHWENKE, NAS Facility, NASA Ames Research Center.
WG02
15 min 2:05
A NEW POTENTIAL ENERGY SURFACE FOR H2 –N2 O AND PIMC SIMULATION PROBING SUPERFLUIDITY
AND VIBRATIONAL FREQUENCY SHIFTS IN DOPED para-H2 CLUSTERS
LECHENG WANG, ROBERT J LE ROY AND PIERRE-NICHOLAS ROY, Guelph-Waterloo Centre for
Graduate Work in Chemistry and Biochemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada;
DAIQIAN XIE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu, China.
WG03
SUPERFLUIDITY HIDDEN IN A FORGOTTEN CORNER
15 min 2:22
TAO ZENG, GREGOIRE GUILLON, and PIERRE-NICHOLAS ROY, Department of Chemistry, University
of Waterloo, Waterloo, Ontario, Canada N2L 3G1.
WG04
15 min 2:39
COMPUTATIONAL FRAMEWORK FOR STUDYING H-BONDING IN THE OH STRETCH REGION OF VIBRATIONAL SPECTRA
LAURA C. DZUGAN and ANNE B. McCOY, Department of Chemistry and Biochemistry, The Ohio State
WG05
15 min 2:56
ESR SPECTRA OF ALKALI-METAL ATOMS ON HELIUM NANODROPLETS: A THEORETICAL MODEL FOR
THE PREDICTION OF HELIUM INDUCED HYPERFINE STRUCTURE SHIFTS
ANDREAS W. HAUSER, Institute of Experimental Physics, Graz University of Technology, Petersgasse
16, A-8010 Graz, Austria; MICHAEL FILATOV, Mulliken Center for Theoretical Chemistry, Institut
für Physikalische und Theoretische Chemie, Universität Bonn, Beringstrasse 4, 53115 Bonn, Germany;
WOLFGANG E. ERNST, Institute of Experimental Physics, Graz University of Technology, Petersgasse 16,
A-8010 Graz, Austria.
WG06
15 min 3:13
Xe AND Rb ATOMS ON HELIUM NANODROPLETS: IS THE VAN DER WAALS ATTRACTION STRONG ENOUGH
TO FORM A MOLECULE?
JOHANNES POMS, ANDREAS W. HAUSER and WOLFGANG E. ERNST, Institute of Experimental
Physics, Graz University of Technology, Petersgasse 16, A-8010 Graz, Austria.
53
Intermission
WG07
15 min 3:45
RENNER-TELLER COUPLING IN OPEN SHELL DIHYDRIDES: A COMPARISON OF THEORY WITH OPTICAL
SPECTRA OF NEUTRAL AND IONIC MOLECULES
G. DUXBURY, Department of Physics, SUPA, John Anderson Building, University of Strathclyde, 107 Rottenrow, Glasgow G4 0NG, Scotland, UK; Ch. JUNGEN, LAC, 1Laboratoire Aime Cotton du CNRS, Universite
de Paris-Sud, 91405 Orsay, France; A. ALIJAH, GSMA, UMR CNRS 6089, Universite de Reims ChampagneArdenne,B.P. 1039, 51687 Reims Cedex 2, France.
WG08
RENNER-TELLER AND SPINORBIT COUPLING IN H2 S+ AND AsH2
15 min 4:02
G. DUXBURY, Department of Physics, SUPA, John Anderson Building, University of Strathclyde, 107 Rottenrow, Glasgow G4 0NG, Scotland,UK ; Ch. JUNGEN, LAC, 1Laboratoire Aime Cotton du CNRS, Universite
de Paris-Sud, 91405 Orsay, France; A. ALIJAH, GSMA, UMR CNRS 6089, Universit de Reims ChampagneArdenne,B.P. 1039, 51687 Reims Cedex 2, France.
WG09
15 min 4:19
COMPUTING ROVIBRATIONAL LEVELS OF POLYATOMIC MOLECULES WITH CURVILINEAR INTERNAL VIBRATIONAL COORDINATES AND AN ECKART FRAME
XIAO-GANG WANG and TUCKER CARRINGTON, JR., Chemistry Department, Queen’s University,
Kingston, Canada.
WG10
AN ACCURATE POTENTIAL ENERGY SURFACE FOR METHANE
15 min 4:36
Kingston, Canada.
WG11
15 min 4:53
THEORETICAL CALCULATIONS AND SIMULATIONS OF INTERACTION OF X-RAYS WITH HIGH-Z
NANOMOITIES FOR USE IN CANCER RADIOTHERAPY
SARA N. LIM, Biophysics Graduate Program; ANIL K. PRADHAN, Biophysics Graduate Program, Chemical Physics Program and Department of Astronomy, The Ohio State University; SULTANA N. NAHAR,
Astronomy, The Ohio State University.
WG12
15 min 5:10
SUPERIORITY OF LOW ENERGY 160 KV X-RAYS COMPARED TO HIGH ENERGY 6 MV X-RAYS IN HEAVY
ELEMENT RADIOSENSITIZATION FOR CANCER TREATMENT
SARA N. LIM, Biophysics Graduate Program; ANIL K. PRADHAN, Biophysics Graduate Program, Departments of Astronomy and Chemistry; SULTANA N. NAHAR, Department of Astronomy; ROLF F. BARTH,
WEILIAN YANG, ROBIN J. NAKKULA, Pathology, The Ohio State University; ALYCIA PALMER and
CLAUDIA TURRO, Department of Chemistry, The Ohio State University.
WG13
ALKYL CH STRETCH VIBRATIONS AS A PROBE OF CONFORMATIONAL PREFERENCES
15 min 5:27
EDWIN L. SIBERT III, Department of Chemistry and Theoretical Chemistry Institute, University of
Wisconsin-Madison, WI 53706; EVAN G. BUCHANAN AND TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN 47907-2084.
54
WG14
THEORETICAL STUDY OF THE VIBRATIONAL SPECTROSCOPY OF THE ETHYL RADICAL
15 min 5:44
DANIEL P. TABOR and EDWIN. L. SIBERT III, Department of Chemistry and Theoretical Chemistry Institute, University of Wisconsin-Madison, Madison, WI 53706.
WG15
15 min 6:01
SIMULATION OF HIGH RESOLUTION VIBRATIONAL AND ELECTRONIC SPECTRA WITH A MULTIFREQUENCY VIRTUAL SPECTROMETER
MALGORZATA BICZYSKO, Center for Nanotechnology Innovation@NEST, Istituto Italiano di Tecnologia,
Piazza San Silvestro 12, I-56127 Pisa, Italy; JULIEN BLOINO, Consiglio Nazionale delle Ricerche, Istituto
di Chimica dei Composti OrganoMetallici (ICCOM-CNR), UOS di Pisa, Area della Ricerca CNR, Via G.
Moruzzi 1, I-56124 Pisa, Italy; VINCENZO BARONE, Scuola Normale Superiore, Piazza dei Cavalieri 7,
I-56126 Pisa, Italy.
55
WH. MICROWAVE
Chair: NICHOLAS WALKER, Newcastle University, Newcastle-upon-Tyne, United Kingdom
WH01
THE LATEST REVISION OF THE ERHAM CODE
15 min 1:30
P. GRONER, Department of Chemistry, University of Missouri-Kansas City, Kansas City, MO 64110-2499.
WH02
10 min 1:47
GENERALIZED EQUATIONS FOR THE INERTIAL TENSOR OF A WEAKLY BOUND COMPLEX
KENNETH R. LEOPOLD, Department of Chemistry, University of Minnesota, 207 Pleasant St., SE, Minneapolis, MN 55455.
WH03
SECOND MOMENTS (PLANAR MOMENTS) AND THEIR APPLICATION IN SPECTROSCOPY
15 min 1:59
ROBERT K. BOHN, Dept. of Chemistry, Univ. of Connecticut, Storrs, CT 06269-3060; JOHN A. MONTGOMERY, JR., H. HARVEY MICHELS, JASON N. BYRD, Dept. of Physics, Univ. of Connecticut, Storrs,
CT 06269-3046.
WH04
15 min 2:16
AN EMPIRICAL APPROACH TO OBTAINING ACCURATE MOLECULAR ROTATIONAL CONSTANTS FOR
ISOTOPICALLY-SUBSTITUTED SPECIES FROM AB INITIO CALCULATIONS
BRETT A. McGUIRE, P. BRANDON CARROLL, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125; GEOFFREY A. BLAKE, Division of Chemistry and
Chemical Engineering and Division of Geological and Planetary Sciences, California Institute of Technology,
Pasadena, CA 91125.
WH05
15 min 2:33
SINGULAR VALUE DECOMPOSITION-BASED MODELING OF TIME DOMAIN SIGNALS IN BROADBAND MICROWAVE SPECTROSCOPY
A. J. MINEI, Department of Chemistry and Biochemistry, Division of Natural Sciences, College of Mount
Saint Vincent, 6301 Riverdale Avenue, Riverdale, New York, 10471; S. A. COOKE, School of Natural and
Social Sciences, Purchase College SUNY, 735 Anderson Hill Road, Purchase, NY 10577, USA.
WH06
15 min 2:50
PURE ROTATIONAL SPECTROSCOPY OF ASYMMETRIC TOPS IN THE UNDERGRADUATE CLASSROOM OR
LABORATORY
56
WH07
15 min 3:07
A NEW E-BAND (60 - 90 GHz) FOURIER TRANSFORM MILLIMETER-WAVE SPECTROMETER
WH08
15 min 3:24
THE FOURIER TRANSFORM MICROWAVE/MILLIMETER SPECTRUM OF ScO (X Σ )
2
+
D. T. HALFEN, J. MIN, and L. M. ZIURYS, Department of Chemistry, Department of Astronomy, and Steward Observatory, University of Arizona, Tucson, AZ 85721.
Intermission
WH09
15 min 4:00
SUBMILLIMETER SPECTROSCOPIC DIAGNOSTICS IN A SEMICONDUCTOR PROCESSING PLASMA
YASER H. HELAL, CHRISTOPHER F. NEESE, JENNIFER A. HOLT, FRANK C. DE LUCIA, Department
of Physics, The Ohio State University, Columbus, OH 43210; PAUL R. EWING, Applied Materials, Austin,
TX 78724; PHILLIP J. STOUT, MICHAEL D. ARMACOST, Applied Materials, Sunnyvale, CA 94085.
WH10
15 min 4:17
IR/THZ DOUBLE RESONANCE SPECTROSCOPY APPROACH FOR REMOTE CHEMICAL DETECTION AT ATMOSPHERIC PRESSURE
ELIZABETH A. TANNER and DANE J. PHILLIPS, IERUS Technologies, 2904 Westcorp Blvd Ste 210,
Huntsville, AL 35805; FRANK C. DE LUCIA, Department of Physics, 191 Woodruff Ave. Ohio State University, Columbus, OH 43210; HENRY O. EVERITT, Army Aviation and Missile RD&E Center, Redstone
Arsenal, AL 35898.
WH11
15 min 4:34
A MICRO-CANTILEVER BASED PHOTOACOUSTIC DETECTOR OF TERAHERTZ RADIATION FOR CHEMICAL
SENSING
NATHAN E. GLAUVITZ, RONALD A. COUTU JR., Department of Electrical and Computer Engineering, Air Force Institute of Technology, 2950 Hobson Way, Wright-Patterson AFB, OH 45433, USA;
MICHAEL N. KISTLER, RYAN F. HAMILTON, DOUGLAS T. PETKIE, IVAN R. MEDVEDEV, Department of Physics, Wright State University, 3640 Colonel Glenn Highway, Dayton, OH 45435, USA.
WH12
15 min 4:51
A TWO-COLOR FOURIER TRANSFORM MM-WAVE SPECTROMETER FOR GAS ANALYSIS OPERATING FROM
260-295 GHZ
AMANDA L. STEBER, BRENT J. HARRIS , KEVIN K. LEHMANN, and BROOKS H. PATE, Department
of Chemistry, University of Virginia, Charlottesville, VA 22904.
WH13
GAS ANALYSIS BY FOURIER TRANSFORM MM-WAVE SPECTROSCOPY
15 min 5:08
BRENT J. HARRIS, AMANDA L. STEBER, KEVIN K. LEHMANN, and BROOKS H. PATE, Department
57
WH14
15 min 5:25
A SEGMENTED CHIRPED-PULSE FOURIER TRANSFORM MM-WAVE SPECTROMETER (260-295 GHZ) WITH
REAL-TIME SIGNAL AVERAGING CAPABILITY
BRENT J.HARRIS, AMANDA L. STEBER, and BROOKS H. PATE, Department of Chemistry, University
of Virginia, Charlottesville, VA 22904.
WH15
15 min 5:42
COHERENT SYNCHROTRON RADIATION FOR ROTATIONAL SPECTROSCOPY: APPLICATION TO THE ROTATIONAL SPECTRUM OF PROPYNAL IN THE 200-750 GHz RANGE
J. BARROS, P. ROY, Synchrotron SOLEIL, L’Orme des Merisiers Saint-Aubin, 91192 Gif-sur-Yvette, France;
D. APPADOO, D. Mc NAUGHTON, Australian Synchrotron Light Source, 800 Blackburn Road Victroria
3168 and Monash University, School of Chemistry, Clayton, Victoria 3800 Australia.; E. ROBERTSON, La
Trobe University, Department of Chemistry, Victoria, 3086, Australia; L. MANCERON, Laboratoire LADIR,
CNRS, Université Pierre et Marie Curie, 75252 Paris Cedex, France.
WH16
DEVELOPMENT OF A REDUCED-COST CHIRPED PULSE MICROWAVE SPECTROMETER
15 min 5:59
IAN A. FINNERAN, DANIEL B. HOLLAND, P. BRANDON CARROLL, Department of Chemistry, California Institute of Technology, Pasadena, CA 91125; and GEOFFREY A. BLAKE, Divisions of Geological
& Planetary Sciences and Chemistry & Chemical Engineering, California Institute of Technology, Pasadena,
CA 91125.
58
WI. INFRARED/RAMAN
Chair: REBECCA PEEBLES, Eastern Illinois University, Charleston, IL
WI01
15 min 1:30
INFRARED SPECTROSCOPIC INVESTIGATION ON HIGH ACIDITY OF DIETHYLETHER CATION
TOMOYA ENDO,YOSHIYUKI MATSUDA,ASUKA FUJII, Depertment of Chemistry, Graduate School of
Science,Tohoku University, Sendi 980-8578, Japan; KAITO TAKAHASHI, Institute of Atomic and Molecular
Sciences, Academia Sinca,Taipei 10617, Taiwan.
WI02
15 min 1:47
STRUCTURAL, CONFORMATIONAL AND VIBRATIONAL STUDIES OF ISOCYANOCYCLOPENTANE FROM
INFRARED, RAMAN SPECTRA AND AB INITIO CALCULATIONS
DATTATRAY K. SAWANT, JOSHUA J. KlAASSEN, JAMES R. DURIG, DEPARTMENT OF CHEMISTRY,
UNIVERSITY OF MISSOURI-KANSAS CITY, MO 64110 USA.
WI03
15 min 2:04
MICROWAVE AND INFRARED SPECTRA, ADJUSTED R0 STRUCTURAL PARAMETERS, CONFORMATIONAL
STABILITIES, VIBRATIONAL ASSIGNMENTS, AND AB INITIO CALCULATIONS OF CYCLOBUTYLCARBOXYLIC ACID CHLORIDE
JOSHUA J. KLAASSEN, PETER GRONER, JAMES R. DURIG, Department of Chemistry, University of
Missouri-Kansas City, Kansas City, MO 64110 USA.
WI04
15 min 2:21
LOWERING OF KETO-ENOL TAUTOMERIZATION BARRIER OF CYCLIC DIKETONES VIA CH· · · O INTERACTION
T. CHAKRABORTY, B. BANDYOPADHYAY, P. BANERJEE and P. PANDEY, Department of Physical
Chemistry, Indian Association for the cultivation of science, Calcutta 700032, India. E-mail: [email protected].
WI05
15 min 2:38
A SPECTROSCOPIC AND THEORETICAL STUDY OF WEAK INTRAMOLECULAR OH· · · π INTERACTIONS IN
ALLYL CARBINOL AND METHALLYL CARBINOL
SIDSEL D. SCHROEDER, KASPER MACKEPRANG, HENRIK G. KJAERGAARD, Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen .
Intermission
WI06
VIBRATIONAL SPECTROSCOPIC INVESTIGATION AND CONFORMATIONAL
HEPTYLAMINE: A COMPARATIVE DENSITY FUNCTIONAL STUDY
10 min 3:15
ANALYSIS OF 1-
MAHIR TURSUN, Department of Physics, Dumlupinar University, Kutahya, 43100, Turkey; and GURKAN
KESAN, Institute of Physics and Biophysics, Faculty of Science, University of South Bohemia, Branisovská
31, Ceské Budéjovice, 370 05, Czech Republic; and CEMAL PARLAK, Department of Physics, Dumlupinar
University, Kutahya, 43100, Turkey; MUSTAFA SENYEL, Science Faculty, Department of Physics, Anadolu
University, Eskisehir, Turkey 26470.
59
WI07
15 min 3:27
LOWEST ENERGY VIBRATIONAL MODES OF NINE NAPHTHALENE DERIVATIVES; EXPERIMENT AND THEORY
M. A. MARTIN-DRUMELa , O. PIRALI, Y. LAQUAISb , Institut des Sciences Moléculaires d’Orsay, CNRS,
UMR 8214, Université Paris XI, bât. 210, 91405 Orsay Cedex, France; SOLEIL Synchrotron, AILES
beamline, L’orme des Merisiers, Saint-Aubin, 91192 Gif-Sur-Yvette, France; C. FALVO, P. PARNEIX and
PH. BRECHIGNAC, Institut des Sciences Moléculaires d’Orsay, CNRS, UMR 8214, Université Paris XI, bât.
210, 91405 Orsay Cedex, France.
a Present
b Present
address: LPCA, EA 4493, Université du Littoral Côte d’Opale, 59140 Dunkerque, France
address: CEA, IRAMIS, SPAM, Lab. Francis Perrin, 91192 Gif-sur-Yvette, France
WI08
10 min 3:44
TOWARD COMPUTATIONAL SPECTROSCOPY STUDIES FOR LARGE MOLECULAR SYSTEMS
WI09
15 min 3:56
DETERMINATION
OF
STRUCTURAL
AND
VIBRATIONAL
PROPERTIES
OF
5QUINOLINECARBOXALDEHYDE USING EXPERIMENTAL FT-IR, FT-RAMAN TECHNIQUES AND THEORETICAL HF AND DFT METHODS
MUSTAFA KUMRU, MUSTAFA KOCADEMIR, TAYYIBE BARDAKCI, Department of Physics, Faculty
of Arts and Sciences, Fatih University, 34500 Buyukcekmece, Istanbul, Turkey.
WI10
15 min 4:13
CYCLIC CONSTRAINTS ON CONFORMATIONAL FLEXIBILITY IN γ-PEPTIDES: CONFORMATION-SPECIFIC
IR AND UV SPECTROSCOPY
PATRICK S. WALSH, RYOJI KUSAKA and TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette. IN 47907; BRIAN F. FISHER and SAMUEL H. GELLMAN, Department of Chemistry, University of Wisconsin-Madison, Madison, WI 53706.
WI11
15 min 4:30
CONFORMATION-SPECIFIC UV and IR SPECTROSCOPY OF CONFORMATIONALLY CONSTRAINED α/γ PEPTIDE FOLDAMERS
RYOJI KUSAKA, Department of Chemistry, Purdue University, West Lafayette, IN 47907, and Department of Chemistry, Graduate School of Science, Hiroshima University, Higashi-Hiroshima, 739-8526, Japan;
DI ZHANG, PATRICK WALSH, JOSEPH GORD, and TIMOTHY S. ZWIER, Department of Chemistry,
Purdue University, West Lafayette, IN 47907; BRIAN F. FISHER, and SAMUEL H. GELLMAN, Department
of Chemistry, University of Wisconsin, Madison, WI 53706.
WI12
15 min 4:47
MIXED CYCLIC CONSTRAINTS ON CONFORMATIONAL FLEXIBILITY IN β/γ-PEPTIDES: CONFORMATION
SPECIFIC IR AND UV SPECTROSCOPY
JOSEPH R. GORD, PATRICK S. WALSH, and TIMOTHY S. ZWIER, Department of Chemistry, Purdue
University, West Lafayette. IN 47907; BRIAN F. FISHER and SAMUEL H. GELLMAN, Department of
Chemistry, University of Wisconsin-Madison, Madison, WI 53706.
60
WI13
15 min 5:04
ACTION IRMPD SPECTROSCOPY OF B2 FRAGMENT IONS FROM QAXIG AND NAXIG PENTAPEPTIDES
L. MORRISON, Department of Chemistry, The Ohio State University, Columbus, OH 43210; J. CHAMOTROOKE, Department of Mass Spectrometry and Proteomics Research, Pasteur Institute, Paris, France;
V. WYSOCKI, Department of Chemistry, The Ohio State University, Columbus, OH 43210.
WI14
15 min 5:21
MODIFCATION OF THE PROLYL RING OF VAL-PRO-ALA AND THE IMPACT OF THIS MODIFICATION ON B2
ION STRUCTURE
MATTHEW C. BERNIER, VICKI H. WYSOCKI, THE OHIO STATE UNIVERSITY, COLUMBUS, OH;
ASHLEY GUCINSKI, U. S. FDA, SAINT LOUIS, MO; JULIA CHAMOT-ROOKE, INSTITUT PASTEUR,
PARIS, FRANCE.
61
WJ. RADICALS AND IONS
Chair: MITCHIO OKUMURA, California Institute of Technology, Pasadena, CA
WJ01
THE INFRARED AND NEAR-INFRARED SPECTRUM OF HNO TRAPPED IN SOLID NEON
15 min 1:30
WJ02
A NEW TYPE OF VIBRONIC INTERACTION IN THE NITRATE FREE RADICAL NO3
15 min 1:47
E. HIROTA, The Graduate University for Advanced Studies, Hayama, Kanagawa 240-0193, Japan.
WJ03
15 min 2:04
DISPERSED FLUORESCENCE SPECTROSCOPY OF THE B̃ E – X̃
and 15 NO3
2
′
2
A′2
TRANSITION OF JET COOLED 14 NO3
MASARU FUKUSHIMA and TAKASHI ISHIWATA, Faculty of Information Sciences, Hiroshima City University, Asa-Minami, Hiroshima 731-3194, Japan.
WJ04
15 min 2:21
ROTATIONALLY-RESOLVED HIGH-RESOLUTION LASER SPECTROSCOPY AND MAGNETIC EFFECT OF THE
B ← X TRANSITION OF NO3 RADICAL
K. TADA, W. KASHIHARA, S. KASAHARA, Graduate School of Science, Kobe University, Kobe 657-8501,
Japan; M. BABA, Graduate School of Science, Kyoto University, Kyoto 606-8502, Japan; T. ISHIWATA,
Graduate School of Information Sciences, Hiroshima City University, Hiroshima 731-3194, Japan; and E. HIROTA, The Graduate University for Advanced Studies, Kanagawa 240-0193, Japan.
WJ05
15 min 2:38
e2
VIBRONIC ANALYSIS OF THE A E STATE OF NO3 RADICAL
′′
TERRANCE J. CODD, MOURAD ROUDJANE, MING-WEI CHENa , and TERRY A. MILLER, Laser Spectroscopy Facility, The Ohio State University, Columbus, Ohio 43210.
a Present
WJ06
address: University of Illinois at Urbana-Champaign, Urbana, IL 61801
15 min 2:55
HIGH RESOLUTION CAVITY RING DOWN SPECTROSCOPY OF THE 310 and 310 410 BANDS OF THE Ã2 E′′ STATE
OF NO3 RADICAL
MOURAD ROUDJANE, TERRANCE J. CODD and TERRY A. MILLER, Laser Spectroscopy Facility, The
Ohio State University, Columbus, Ohio 43210.
62
WJ07
15 min 3:12
THE RENNER-TELLER AND JAHN-TELLER EFFECTS IN PROTOTYPICAL MOLECULAR CATIONS SUBJECT
TO A VERY LARGE SPIN-ORBIT COUPLING
BÉRENGER GANS, MONIKA GRÜTTER and FRÉDÉRIC MERKT, Laboratorium für Physikalische
Chemie, ETH Zürich, CH-8093 Zürich, Switzerland.
WJ08
OBSERVATION OF THE a1 CH STRETCHING MODES OF PHENYL RADICAL
15 min 3:29
CHIH-HSUAN CHANG, GRANT T. BUCKINGHAM, DAVID J. NESBITT, JILA, National Institute of Standards and Technology University of Colorado, and Department of Chemistry and Biochemistry University of
Colorado at Boulder, Colorado 80309.
WJ09
15 min 3:46
HIGH RESOLUTION ROVIBRATIONAL SPECTROSCOPY OF JET-COOLED PHENYL RADICAL: THE ν19 OUTOF-PHASE SYMMETRIC C-H STRETCH
GRANT T. BUCKINGHAM, CHIH-HSUAN CHANG, and DAVID J. NESBITT, JILA, National Institute of
Standards and Technology and University of Colorado, Department of Chemistry and Biochemistry, Boulder,
CO 80309.
Intermission
WJ10
MOLECULAR CONSTANTS OF C2 IN THE c
15 min 4:20
3
Σ+
u
STATE
MASAKAZU NAKAJIMA and YASUKI ENDO, Department of Basic Science, The University of Tokyo,
Tokyo 153-8902, Japan.
WJ11
15 min 4:37
RE-ANALYSIS OF THE SPIN-ORBIT PERTURBATION FOR THE PHILLIPS SYSTEM AND THE BALLIKRAMSAY SYSTEM OF THE SPECTRA OF C2
WANG CHEN, JIAN TANG and KENTAROU KAWAGUCHI, Graduate School of Natural Science and Technology Okayama University, 3-1-1 Tsushima-Naka, Okayama 700-8530, Japan.
WJ12
15 min 4:54
THE ETHYL RADICAL IN SUPERFLUID HELIUM NANODROPLETS: ROVIBRATIONAL SPECTROSCOPY AND
AB INITIO CALCLUATIONS
PAUL L. RASTON, CHRISTOPHER P. MORADI, Department of Chemistry, University of Georgia, Athens,
Georgia 30602-2556; JAY AGARWAL, JUSTIN. M. TURNEY, HENRY F. SCHAEFER III, Center for
Computational Chemistry, University of Georgia, Athens, Georgia 30602-2556; GARY E. DOUBERLY,
Department of Chemistry, University of Georgia, Athens, Georgia 30602-2556.
WJ13
15 min 5:11
INRARED SPECTROSCOPY AND TUNNELING DYNAMICS OF THE VINYL RADICAL IN He NANODROPLETS
4
PAUL L. RASTON, TAO LIANG, EMMANUEL I. OBI, and GARY E. DOUBERLY, Department of Chemistry, University of Georgia, Athens, Georgia 30602, USA.
63
WJ14
15 min 5:28
STRUCTURE AND DYNAMICS OF THE CYCLOPROPENE RADICAL CATION STUDIED BY HIGHRESOLUTION PHOTOELECTRON SPECTROSCOPY
KONSTANTINA VASILATOU, JULIE M. MICHAUD, DENITSA BAYKUSHEVA, GUIDO GRASSI and
FREDERIC MERKT, Laboratorium für Physikalische Chemie, ETH Zürich, CH-8093 Zürich, Switzerland.
WJ15
15 min 5:45
STRUCTURE DETERMINATION OF NON-LINEAR HYDROCARBON CHAINS BY DEUTERIUM LABELING
P.O. Box 9513, NL-2300 RA Leiden; M. A. HADDAD, W. UBACHS, LaserLaB, VU University Amsterdam,
De Boelelaan 1081, NL-1081 HV, Amsterdam, The Netherlands.
64
WK. ELECTRONIC
Chair: ANTHONY MERER, Academia Sinica, Taipei, Taiwan
WK01
SPECTROSCOPY OF LiCa AND RbSr MOLECULES ON HELIUM NANODROPLETS
15 min 1:30
WK02
15 min 1:47
SPECTROSCOPY OF Li ATOMS AND Li DIMERS IN THE TRIPLET MANIFOLD ON THE SURFACE OF HELIUM
NANODROPLETS
WK03
10 min 2:04
1
a
OBSERVATION OF THE 5 1 Σ+
u and 5 Πu STATES OF Rb2 BY POLARISATION LABELLING SPECTROSCOPY
JACEK SZCZEPKOWSKI, WODZIMIERZ JASTRZȨBSKI, Institute of Physics, Polish Academy of Sciences, Al. Lotnikóv 32/46, 02-668 Warsaw, Poland ; PAWEŁ KOWALCZYK, ANNA GROCHOLA, Institute
of Experimental Physics, Department of Physics, University of Warsaw, ul. Hoża 69, 00-681 Warsaw, Poland ;
ABDUL-RAHMAN ALLOUCHE, PATRICK CROZET and AMANDA J. ROSS, Institut Lumière Matière,
Université Lyon 1 & CNRS UMR5306, Université de Lyon, France.
a Supported
by the PAN-CNRS exchange programme, 2011-12
WK04
5 min 2:16
DOUBLE RESONANCE EXCITATION OF THE RUBIDIUM DIMER : THE 2 Πg STATE
1
ANASTASIA DROZDOVA, Department of Chemistry, Moscow State University, 119991 Moscow, Russia ;
ABDUL-RAHMAN ALLOUCHE, GHASSAN WANNOUS, PATRICK CROZET and AMANDA J. ROSS,
Institut Lumière Matière, Université Lyon 1 & CNRS UMR5306, Université de Lyon, France.
WK05
15 min 2:23
EXCITATION OF ULTRACOLD MOLECULES TO “TRILOBITE-LIKE" LONG-RANGE MOLECULAR RYDBERG
STATES
M. A. BELLOS, R. CAROLLO, J. BANERJEE, E. E. EYLER, P. L. GOULD, W. C. STWALLEY, Department
of Physics, University of Connecticut, Storrs, CT 06269-3046.
WK06
HIGH RESOLUTION PHOTOELECTRON SPECTROSCOPY OF
15 min 2:40
Au−
2
and
Au−
4
BY PHOTOELECTRON IMAGING
IKER LEON, ZHENG YANG, and LAI-SHENG WANG, DEPARTMENT OF CHEMISTRY, BROWN UNIVERSITY, PROVIDENCE, RI 02912, USA.
65
WK07
15 min 2:57
INTRACAVITY LASER ABSORPTION SPECTROSCOPY OF PLATINUM NITRIDE IN THE NEAR INFRARED
LEAH C. O’BRIEN, KAITLIN A. WOMACK, Department of Chemistry, Southern Illinois University, Edwardsville, IL 62026-1652; JAMES J. O’BRIEN, SEAN WHITTEMORE, Department of Chemistry, University of Missouri, St Louis, MO 63121-4499.
WK08
REANALYSIS OF THE NEAR INFRARED ELECTRONIC TRANSITIONS OF NiCl
10 min 3:14
LEAH C. O’BRIEN, TAYLOR DAHMS, Department of Chemistry, Southern Illinois University, Edwardsville, IL 62026-1652; JAMES J. O’BRIEN, Department of Chemistry, University of Missouri, St Louis,
MO 63121-4499.
WK09
10 min 3:26
INTRACAVITY LASER ABSORPTION SPECTROSCOPY OF ZIRCONIUM FLUORIDE IN THE NEAR INFRARED
LEAH C. O’BRIEN, JACK C. HARMS, Department of Chemistry, Southern Illinois University, Edwardsville,
IL 62026-1652; JAMES J. O’BRIEN , Department of Chemistry and Biochemistry, University of Missouri, St
Louis, MO 63121-4499.
Intermission
WK10
15 min 4:00
ROTATIONAL AND HYPERFINE STRUCTURE IN THE [17.6]2.5−X2.5 AND [23.3]2.5−X2.5 TRANSITIONS OF
IRIDIUM MONOXIDE
C. LINTON, D. W. TOKARYK, Physics Department and Centre for Laser, Atomic and Molecular Sciences,
University of New Brunswick, Fredericton, NB, Canada E3B 5A3; A. G. ADAM, J. A. DAIGLE, L. M. ESSON, A. D. GRANGER, A. M. SMITH, Chemistry Department and Centre for Laser, Atomic and Molecular
Sciences, University of New Brunswick, Fredericton, NB, Canada E3B 5A3; T. C. STEIMLE, Department of
Chemistry and Biochemistry, Arizona State University, Tempe,AZ 85287, USA..
WK11
ELECTRONIC TRANSITIONS OF YTTRIUM MONOXIDE
15 min 4:17
Y.W. NG, NA WANG, ANDREW B. CLARK and A. S-C. CHEUNG, Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong..
WK12
ELECTRONIC TRANSITIONS OF PALLADIUM AND VANADIUM DIMER
10 min 4:34
YUE QIAN, Y.W. NG, and A. S-C. CHEUNG, Department of Chemistry, The University of Hong Kong,
Pokfulam Road, Hong Kong.
WK13
ELECTRONIC TRANSITIONS OF RUTHENIUM MONOXIDE
15 min 4:46
NA WANG, Y. W. NG , and A. S-C. CHEUNG, Department of Chemistry, The University of Hong Kong,
66
WK14
PRECISION SPECTROSCOPY OF TELLURIUM
10 min 5:03
J. COKER, J.E. FURNEAUX, Department of Physics and Astronomy, University of Oklahoma, Norman,
OK 73069.
WK15
15 min 5:15
IONIZATION MEASUREMENT AND SPECTROSCOPY OF ThS AND ThS
+
J. H. BARTLETT, M. C. HEAVEN, Department of Chemistry, Emory University, Atlanta, GA 30322.
WK16
15 min 5:32
A STUDY OF NbCr AND NbCr BY ANION PHOTOELECTRON SPECTROSCOPY
−
MELISSA A. BAUDHUIN, PRAVEENKUMAR BOOPALACHANDRAN, SRIJAY S. RAJAN, and
DOREEN G. LEOPOLD , Department of Chemistry, University of Minnesota, Minneapolis, MN 55455.
67
RA. MINI-SYMPOSIUM: THEORY AND SPECTROSCOPY
THURSDAY, JUNE 20, 2013 – 8:30 AM
Chair: JENS-UWE GRABOW, Gottfried-Wilhelm-Leibniz-Universitaet, Hannover, Germany
RA01
INVITED TALK
30 min 8:30
MANIFESTATIONS OF VIBRONIC COUPLING EFFECTS IN MOLECULAR SPECTROSCOPY: FROM THE
QUENCHING OF EXCITONIC ENERGY SPLITTINGS TO THE CLEMENTS BANDS OF SO2
HORST KÖPPEL, Theoretical Chemistry, Institute of Physical Chemistry, University of Heidelberg, D-69120
Heidelberg, Germany.
RA02
15 min 9:05
TUNNELING SPLITTINGS IN VIBRONIC STRUCTURE OF CH3 F (X̃ E): STUDIED BY HIGH RESOLUTION
PHOTOELECTRON SPECTRA AND AB IN IT IO THEORETICAL METHOD
+
2
YUXIANG MO, SHUMING GAO, ZUYANG DAI, and HUA LI, Department of Physics and State Key Laboratory of Low-Dimensional Quantum Physics, Tsinghua University, Beijing 100084, China.
RA03
15 min 9:22
ANALYSIS OF THE ROTATIONALLY-RESOLVED SPECTRA OF THE VIBRONICALLY-ACTIVE MOLECULES
DMITRY G. MELNIK and TERRY A. MILLER, Laser Spectroscopy Facility, Department of Chemistry, The
Ohio State University, 120 W. 18th Avenue, Columbus, Ohio 43210.
RA04
A THEORETICAL PREDICTION OF ELECTRONIC TRANSITIONS IN C3
15 min 9:39
DAVID W. SCHWENKE, GALINA M. CHABAN, NASA Ames Research Center, Moffett Field, CA 94035.
RA05
15 min 9:56
e 2A′′ AND A
e 2A′ ELECTONIC STATES OF HSO/HOS
THE RENNER EFFECT IN THE X
ROMAN I. OVSYANNIKOV, Institute of Applied Physics, Russian Academy of Science, Ulyanov Street 46,
Nizhny Novgorod, Russia 603950, and Physical and Theoretical Chemistry, Faculty of Mathematics and Natural Sciences, University of Wuppertal, D-42097 Wuppertal, Germany; PER JENSEN, Physical and Theoretical Chemistry, Faculty of Mathematics and Natural Sciences, University of Wuppertal, D-42097 Wuppertal,
Germany; TSUNEO HIRANO, Department of Chemistry, Faculty of Science, Ochanomizu University, 2-1-1
Otsuka, Bunkyo-ku, Tokyo 112-8610, Japan.
Intermission
RA06
15 min
PHOTODISSOCIATION SPECTROSCOPY OF BARE AND HYDRATED PERMANGANATE IONS
10:30
JORGEN HOUMOLLER, KRISTIAN STOCHKEL, STEEN BRONDSTED NIELSEN, Department of
Physics and Astronomy, Aarhus University, Ny Munkegade 120, 8000 Aarhus C, Denmark; SYDNEY H.
KAUFMAN, J. MATHIAS WEBER, JILA, and Department of Chemistry and Biochemistry, University of
Colorado, Boulder, Colorado 80309, USA.
68
RA07
15 min 10:47
MANIFESTATION OF NONADIABATIC EFFECTS IN THE IR SPECTRUM OF PARA-BENZOQUINONE RADICAL
CATION
KRZYSZTOF PIECH, THOMAS BALLY, Department of Chemistry, University of Fribourg, CH-1700 Fribourg, Switzerland; TAKATOSHI ICHINO and JOHN F. STANTON, Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, TX 78712.
RA08
15 min 11:04
NUMERICALLY EXACT DYNAMICS OF FUNCTIONAL QUANTUM SYSTEMS - APPLICATIONS TO GaAs
QUANTUM DOT QUBITS AND 2-DIMENSIONAL SPECTRA OF VERY LARGE PHOTOSYNTHEITC COMPLEXES
NIKESH S. DATTANI, Oxford University, Department of Chemistry, Oxford, OX1 3QZ, UK.
RA09
15 min 11:21
OBSERVATION AND ANALYSIS OF BOUND → FREE TRANSITION OF ScI3 PHOTOEXCITED IN THE ULTRAVIOLET
LOANN D. POMMAREL, J. DARBY HEWITT, THOMAS C. GALVIN, and J. GARY EDEN, Laboratory
for Optical Physics and Enginnering, Department of Electrical and Computer Engineering, University of
Illinois at Urbana-Champaign, 607 East Healey Street, Champaign, IL 61820.
RA10
EXCITED STATES OF THE DIATOMIC MOLECULE CrHe
15 min
11:38
JOHANN V. POTOTSCHNIG, MARTIN RATSCHEK, ANDREAS W. HAUSER and WOLFGANG E. ERNST, Institute of Experimental Physics, TU Graz, Petersgasse 16, 8010 Graz, Austria.
RA11
15 min
11:55
POLARIZATION EFFECTS AND IONIC BONDING IN A POLAR DIATOMIC: THE CaF X Σ STATE
+
1
+
STEPHEN L. COY, JOSHUA H. BARABAN, ROBERT W. FIELD, MIT Dept. of Chemistry, Cambridge, MA
02139; BRYAN M. WONG, Materials Chemistry Dept., Sandia National Lab., Livermore, CA 94551.
69
RB. RADICALS AND IONS
Chair: HEATHER ABBOTT-LYON, Kennesaw State University, Kennesaw, GA
RB01
15 min 8:30
VIBRATIONAL SPECTROSCOPY OF SYMPATHETICALLY COOLED CaH MOLECULAR IONS
+
NCAMISO B. KHANYILE, JAMES E. GOEDERS and KENNETH R. BROWN, Department of Chemistry,
Georgia Institute of Technology, Atlanta, GA 30332.
RB02
INTRACLUSTER REACTIONS IN Ni-CO2 CLUSTERS
15 min 8:47
JONATHON A. MANER, MATTHEW D. McDOWELL and MICHAEL A. DUNCAN, Department of Chemistry, University of Georgia, Athens, Georgia 30602..
RB03
15 min 9:04
INFRARED PHOTODISSOCIATION SPECTROSCOPY OF METAL OXIDE CARBONYL CATIONS.
ANTONIO D. BRATHWAITE, MICHAEL A. DUNCAN, Department of Chemistry, University of Georgia,
Athens, GA 30602-2256; ,.
RB04
15 min 9:21
ACCURATE POTENTIAL ENERGY CURVES FOR THE GROUND ELECTRONIC STATES OF NeH AND ArH+
+
JOHN A. COXON, Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, Canada B3H 4J3;
PHOTOS G. HAJIGEORGIOU, Department of Life and Health Sciences, University of Nicosia, Nicosia 1700,
Cyprus.
RB05
15 min 9:38
EXPANSION DISCHARGE SOURCE FOR ION BEAM LASER SPECTROSCOPY OF COLD MOLECULAR IONS
MICHAEL PORAMBO, JESSICA PEARSON, CRAIG RICCARDO, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801; BENJAMIN J. McCALL, Departments of Chemistry and Astronomy, University of Illinois at Urbana-Champaign, Urbana, IL 61801.
Intermission
RB06
15 min
INFRARED PHOTODISSOCATION SPECTROSCOPY OF METAL BENZENE CATION COMPLEXES
10:15
K. N. REISHUS, M. A. DUNCAN, Department of Chemistry, University of Georgia, Athens, GA 30602-2256.
RB07
15 min 10:32
SPECTROSCOPY OF BENZYL-TYPE RADICALS GENERATED BY ELECTRIC DISCHARGE : JET-COOLED
DICHLOROBENZYL RADICALS
YOUNG WOOK YOON and SANG KUK LEE, Department of Chemistry, Pusan National University, Pusan
609-735, Republic of Korea.
70
RB08
15 min
10:49
ROVIBRATIONAL SPECTROSCOPY OF THE OH-O3 AND C2 H4 -O3 COMPLEXES IN He NANODROPLETS
4
EMMANUEL I. OBI, and GARY E. DOUBERLY, Department of Chemistry, University of Georgia, Athens,
Georgia 30602, USA.
RB09
SPECTROSCOPY OF THE CH3 -HCL COMPLEX IN HELIUM NANODROPLETS
15 min
11:06
CHRISTOPHER P. MORADI and GARY E. DOUBERLY, Department of Chemistry, University of Georgia, Athens, Georgia 30602-2556.
RB10
15 min 11:23
BIMOLECULAR PYROLYSIS REACTIONS STUDIED BY CHIRPED-PULSE MILLIMETER-WAVE SPECTROSCOPY
KIRILL PROZUMENT, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA
02139; ANGAYLE K. VASILIOU, Department of Chemistry and Biochemistry, University of Colorado at
Boulder, Boulder, CO 80309; RACHEL G. SHAVER, G. BARRATT PARK, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139; JOHN S. MUENTER, Department of Chemistry,
University of Rochester, Rochester, NY 14627; JOHN F. STANTON, Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, TX 78712; G. BARNEY ELLISON, Department of Chemistry
and Biochemistry, University of Colorado at Boulder, Boulder, CO 80309; ROBERT W. FIELD, Department
of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139.
RB11
5 min 11:40
SLOW PHOTOELECTRON SPECTROSCOPY AND STATE-SELECTED UNIMOLECULAR DECOMPOSITION OF
IONIZED DNA BASES ANALOGUES
AHMED MAHJOUB and MAJDI HOCHLAF, Universite Paris-Est, Laboratoire Modelisation et Simulation
Multi Echelle, MSME UMR 8208 CNR, 77454 Marne la vallee (France); LIONEL POISSON, Laboratoire
Francis Perrin CNR- URA 2453, CEA –IRAMIS, 91192, Gif sur Yvette (France); GUSTAVO A. GARCIA and
LAURENT NAHON, Synchrotron SOLEIL, LOrme des Merisiers, Saint Aubin BP 48, 91193 (France).
RB12
15 min 11:47
INSIGHTS ON HYDROGEN LIBERATION FROM WATER USING ANIONIC TRANSITION METAL OXIDE CLUSTERS: A COMBINED COMPUTATIONAL AND SPECTROSCOPIC STUDY
RAGHUNATH O. RAMABHADRAN, JENNIFFER E. MANN, SARAH. E. WALLER, DAVID W.
ROTHGEB, CAROLINE C. JARROLD, KRISHNAN RAGHAVACHARI, DEPARTMENT OF CHEMISTRY,
INDIANA UNIVERSITY, BLOOMINGTON, IN-47405.
71
RC. MICROWAVE
Room: 1000MCPHERSON LAB
Chair: ROBERT BOHN, University of Connecticut, Storrs, CT
RC01
THE ROTATIONAL SPECTRUM OF RUTHENIUM MONOCARBIDE USING PPMODRa
15 min 8:30
AZ 85287; ALLAN G. ADAM, Center for Lasers, Atomic and Molecular Sciences and Physics Department,
University of New Brunswick, Fredericton, NB Canada E3B 5A3.
a Funded
by DoE-BES
RC02
15 min 8:47
PURE ROTATIONAL SPECTRA OF THE REACTION PRODUCTS OF LASER ABLATED THORIUM METAL AND
OXYGEN MOLECULES ENTRAINED WITHIN SUPERSONIC EXPANSIONS OF NOBLE GASES
B. E. LONG, Department of Chemistry, Wesleyan University, 52 Lawn Avenue, Middletown, Connecticut,
06459; S. A. COOKE, School of Natural and Social Sciences, Purchase College SUNY, 735 Anderson Hill
Road, Purchase, NY 10577, USA.
RC03
DETECTION OF THE ROTATIONAL SPECTRUM OF SULFOXYLIC ACID (HOSOH)
15 min 9:04
KYLE N. CRABTREE, OSCAR MARTINEZ, JR., LOU BARREAUa and MICHAEL C. McCARTHY,
Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, 02138; SVEN THORWIRTH, I. Physikalisches Institut, Universität zu Köln, 50937 Köln, Germany.
a Present
address: École Normale Supérieure de Cachan, 94235 Cachan Cedex, France
RC04
15 min 9:21
GLOBAL ANALYSIS OF BROADBAND ROTATION AND VIBRATION-ROTATION SPECTRA OF SULFUR DICYANIDE
Poland; MANFRED WINNEWISSSER, BRENDA P. WINNEWISSER, FRANK C. DE LUCIA, Department
of Physics, The Ohio State University, Columbus, OH 43210, USA; DENNIS W. TOKARYK, Department of
Physics and Centre for Laser, Atomic, and Molecular Sciences, University of New Brunswick, P.O.Box. 4400,
New Brunswick E3B 5A3, Canada; BRANT E. BILLINGHURST, Canadian Light Source Inc., University of
Saskatchewan, 101 Perimeter Road, Saskatoon, Saskatchewan S7N 0X4, Canada.
RC05
15 min 9:38
CONTINUATION OF THE PURSUIT OF THE FAR-INFRARED SPECTRUM OF NCNCS, AT THE CANADIAN
LIGHT SOURCE
FRANK C. DE LUCIA, DeMANFRED WINNEWISSER, BRENDA P. WINNEWISSER,
partment of Physics, The Ohio State University, Columbus Ohio, 43210-1106, USA; DENNIS W. TOKARYK, STEPHEN C. ROSS, Department of Physics and Centre for Laser, Atomic, and
Molecular Sciences, University of New Brunswick, P.O. Box 4400, Fredericton NB E3B 5A3, Canada;
BRANT E. BILLINGHURST, Canadian Light Source Inc., University of Saskatchewan, 101 Perimeter Road,
Saskatoon, Saskatchewan S7N 0X4,Canada.
72
RC06
15 min 9:55
TERAHERTZ SPECTROSCOPY OF CaH (X Σ ), MgH (X Σ ), AND ZnH (X Σ ) : EXTREME HYDRIDE SYNTHESIS
2
+
2
+
2
+
MATTHEW P. BUCCHINO, Department of Chemistry and Biochemistry, University of Arizona, Tucson, Arizona 85721; and LUCY M. ZIURYS, Department of Chemistry and Biochemistry, Department of Astronomy,
and Steward Observatory, University of Arizona, Tucson, Arizona 85721.
Intermission
RC07
15 min 10:30
THE MILLIMETER DIRECT ABSORPTION AND FOURIER TRANSFORM MICROWAVE SPECTRUM OF VANADIUM SULFIDE (X4 Σ− )
GILLES ADANDE, L.M. ZIURYS, Department of Chemistry, Steward Observatory University of Arizona,
Tucson, 85721.
RC08
15 min
10:47
MILLIMETER AND SUB-MILLIMETER SPECTROSCOPY OF CRCCH (X Σ )
6
+
JIE MIN, LUCY. M. ZIURYS, Department of Chemistry and Biochemistry, Department of Astronomy, and
Steward Observatory, University of Arizona, Tucson, AZ 85721.
RC09
15 min
CHARACTERIZATION OF SILICON SULFIDES BY CHIRPED-PULSE ROTATIONAL SPECTROSCOPY
11:04
MICHAEL C. McCARTHY, KYLE N. CRABTREE, OSCAR MARTINEZ, JR., Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138, and School of Engineering and Applied Sciences, Harvard University, 29 Oxford Street, Cambridge, MA 02138.
RC10
15 min 11:21
DETECTION OF TWO HIGHLY-STABLE SILICON NITRIDES BY CHIRPED-PULSE ROTATIONAL SPECTROSCOPY: HSiNSi and SiH3 NSi
RC11
FOURIER-TRANSFORM MICROWAVE SPECTROSCOPY OF HCCNSi AND NCNSi
15 min
11:38
S. THORWIRTH, I. Physikalisches Institut, Universität zu Köln, 50937 Köln, Germany; R. I. KAISER, Department of Chemistry, University of Hawaii at Manoa, Honolulu, HI 96822, U.S.A.; M. C. MCCARTHY, K.
N. CRABTREE, O. MARTINEZ, JR., Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138, U.S.A. and School of Engineering and Applied Sciences, Harvard University, 29 Oxford
Street, Cambridge, MA 02138, U.S.A.
RC12
15 min 11:55
SUBSTITUTION STRUCTURES OF MULTIPLE SILICON-CONTAINING SPECIES BY CHIRPED PULSE FTMW
SPECTROSCOPY
NATHAN A. SEIFERT, SIMON LOBSIGER, BROOKS H. PATE, Department of Chemistry, University of
Virginia, McCormick Rd., Charlottesville, VA 22904-4319; GAMIL A. GUIRGIS, JASON S. OVERBY,
Department of Chemistry & Biochemistry, College of Charleston, Charleston, SC 29424 USA; JAMES R.
DURIG, Department of Chemistry, University of Missouri-Kansas City, Kansas City, MO 64110 USA.
73
RD. ELECTRONIC
Chair: ALLAN S. C. CHEUNG, University of Hong Kong, Hong Kong
RD01
METHODS FOR MANIPULATING CaF USING OPTICAL POLYCHROMATIC FORCES
15 min 8:30
EDWARD E. EYLER, SCOTT E. GALICA, and LELAND M. ALDRIDGE, Department of Physics, University of Connecticut, Storrs, CT 06269, USA.
RD02
15 min 8:47
NEW LINE LISTS INCLUDING INTENSITIES FOR THE C2 SWAN SYSTEM (d Πg -a Πu ), C2 SINGLET SYSTEMS
AND ROVIBRATIONAL TRANSITIONS WITHIN THE NH X3 Σ− GROUND STATE.
3
3
J. S. A. BROOKE, Department of Chemistry, University of York, York, UK; P. F. BERNATH, Department
of Chemistry & Biochemistry, Old Dominion University, Norfolk, VA, USA; C. M. WESTERN, School of
Chemistry, University of Bristol, Bristol, UK; T. W. SCHMIDT and G. B. BACSKAY, School of Chemistry, The
University of Sydney, New South Wales, Australia; M. C. VAN HEMERT, Department of Chemistry, Gorlaeus
Laboratories, Leiden University, The Netherlands; G. C. GROENENBOOM, Theoretical Chemistry, Institute
for Molecules and Materials (IMM), Radboud University Nijmegen, Nijmegen, The Netherlands.
RD03
15 min 9:04
MEASUREMENT OF ABSOLUTE HYDROXYL RADICAL CONCENTRATION IN LEAN FUEL-AIR MIXTURES
EXCITED BY NANOSECOND PULSED DISCHARGEa .
Z. YIN, W. R. LEMPERT, I. V. ADAMOVICH, The Ohio State University, Dept. of Mechanical and
Aerospace Engineering, Columbus, OH 43210.
a Funded
by AFOSR MURI for plasma assisted combustion research grant
RD04
15 min 9:21
LASER INDUCED FLUORESCENCE SPECTROSCOPY OF JET COOLED SiCN : ROTATIONAL ANALYSIS OF
THE HOT BANDS
RD05
THE ELECTRIC DIPOLE MOMENT OF IRIDIUM MONOSILICIDE, IrSi
15 min 9:38
ANH LE AND TIMOTHY C. STEIMLE, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ 85287; LAN CHENG AND JOHN F. STANTON, The University of Texas at Austin, Austin,
TX 78712-0165.
RD06
15 min 9:55
TRIPLE-SINGLET MIXING in Si3 : the 1
3
A′′1
-ã
3
A′2
TRANSITION
a
RUOHAN ZHANG, AND TIMOTHY C. STEIMLE, Department of Chemistry and Biochemistry, Arizona
State University, Tempe, AZ 85287.
a Funded
by the NSF
74
RD07
MULTIPLEXED MODR WITH APPLICATIONS TO THE ELECTRONIC SPECTRUM OF SO2
15 min
10:12
G. BARRATT PARK and ROBERT W. FIELD, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139; ANDREW R. WHITEHILL and SHUHEI ONO, Department of Earth, Atmospheric, and Planetary Sciences, Massachusetts Institute of Technology, Cambridge, MA 02139.
Intermission
RD08
15 min
10:45
SPECTROSCOPY OF THE NO-Ar COMPLEX IN THE VICINITY OF THE 3p ← X Π TRANSITIONS IN NITRIC
OXIDE
2
JOE P. HARRIS, TIMOTHY G. WRIGHT, ADRIAN M. GARDNER, ANNA ANDREJEVA,
NICHOLAS A. BESLEY and OLGA V. ERSHOVA, School of Chemistry, University Park, University
of Nottingham, NG7 2RD, United Kingdom; JACEK KLOS, Department of Chemistry, University of
Maryland, College Park, MD 20742.
RD09
15 min
AN INTRODUCTION TO HIGH RESOLUTION COHERENT MULTIDIMENSIONAL SPECTROSCOPY
11:02
PETER C. CHEN, THRESA A. WELLS, and ZURI R. HOUSE, Spelman College Chemistry Department,
350 Spelman Lane, Atlanta, GA 30314; and BENJAMIN R. STRANGFELD, Department of Chemistry and
Chemical Biology, Georgia Institute of Technology, Atlanta, GA 30332.
RD10
15 min 11:19
STRATEGIES FOR INTERPRETING HIGH RESOLUTION COHERENT MULTIDIMENSIONAL SPECTRA
THRESA A. WELLS, ZURI R. HOUSE, and PETER C. CHEN, Spelman College Chemistry Department, 350
Spelman Lane, Atlanta, GA 30314; BENJAMIN R. STRANGFELD, Department of Chemistry and Chemical
Biology, Georgia Institute of Technology, Atlanta, GA 30332.
RD11
HIGH RESOLUTION COHERENT 3D SPECTROSCOPY OF BROMINE
15 min
11:36
BENJAMIN R. STRANGFELD, Department of Chemistry and Chemical Biology, Georgia Institute of Technology, Atlanta, GA 30332; THRESA A. WELLS, ZURI R. HOUSE, and PETER C. CHEN, Spelman College
Chemistry Department, 350 Spelman Lane, Atlanta, GA 30314.
RD12
HIGH RESOLUTION COHERENT THREE-DIMENSIONAL SPECTROSCOPY OF IODINE
10 min
11:53
ZURI R. HOUSE, THRESA A. WELLS, and PETER C. CHEN, Spelman College Chemistry Department,
75
RE. MINI-SYMPOSIUM: SPECTROSCOPY OF PLANETARY
ATMOSPHERES
Chair: VINCENT BOUDON, CNRS/Université de Bourgogne, Dijon, France
RE01
INVITED TALK
30 min 8:30
SATELLITE REMOTE SENSING OF THE REACTIVE LOWER ATMOSPHERE USING MEDIUM RESOLUTION
INFRARED MEASUREMENTS: HIGHLIGHTS FROM IASI MISSION
P.F. COHEUR, Atmospheric Spectroscopy / Quantum Chemistry and Photophysics, Université Libre de Bruxelles CP160/09, Brussels, Belgium.
RE02
THE REVISED METHANE DATABASE IN HITRAN 2012
15 min 9:05
LINDA R. BROWN, Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Dr.,
Pasadena, CA 91109.
RE03
HITRAN2012 AND REMOTE SENSING OF PLANETARY ATMOSPHERES
15 min 9:22
I. E. GORDON, L. S. ROTHMAN, G. LI, Harvard-Smithsonian Center for Astrophysics, Atomic and Molecular Physics Division, Cambridge MA 02138-1516, USA.
RE04
COSMIC-RAY IONIZATION AND HAZES ON HOT JUPITERS
15 min 9:39
PAUL B RIMMER, CHRISTIANE HELLING, SUPA, School of Physics and Astronomy, University of St
Andrews, KY16 9SS; CATHERINE WALSH, Leiden Observatory, P.O. Box 9513, NL-2300 RA Leiden, The
Netherlands.
RE05
SPECTROSCOPY FOR HOT SUPER-EARTH EXOPLANETS
15 min 9:56
P.F. BERNATH and M. DULICK, Department of Chemistry & Biochemistry, Old Dominion University, 4541
Hampton Boulevard, Norfolk, VA, 23529-0126, USA.
Intermission
RE06
10 min 10:30
SPECTROSCOPIC STUDY OF CYANOACETYLENE CATION: SLOW PHOTO-ELECTRON SPECTROSCOPY AND
AB-INITIO INVESTIGATIONS
AHMED MAHJOUB, MARTIN SCHWELL, YVES BENILAN, NICOLAS FRAY and MARIE-CLAIRE
GAZEAU, LISA UMR CNRS 7583, Univ. Paris Est Creteil & Univ. Paris Diderot, Institut Pierre Simon
Laplace,61 Ave du General de Gaulle, 94010, Creteil, France; GUSTAVO A. GARCIA and FRANCOIS
GAIE-LEVERL, Synchrotron SOLEIL, L’Orme des Merisiers, St.Aubin, B.P. 48, 91192, Gif-sur-Yvette Cedex,
France; NORBERT CHAMPION and SYDNEY LEACH, LERMA UMR CNRS 8112, Observatoire de ParisMeudon, 5 place Jules-Jansen, 92195, Meudon, France.
76
RE07
15 min
THE ν12 + ν6 − ν6 AND ν11 − ν12 BANDS OF
THE FOUR LOWEST VIBRATIONAL STATES
12
CH13
3 CH3 :
10:42
A FREQUENCY ANALYSIS INCLUDING DATA FROM
N. MOAZZEN-AHMADI, J. NOROOZ OLIAEE, Department of Physics and Astronomy, University of Calgary, 2500 University Dr., N.W., Calgary, Alberta T2N 1N4, Canada; V.-M. HORNEMAN, Department of
Physical Sciences, University of Oulu, P.O. Box 3000, Fin-90014 Oulu, Finland.
RE08
15 min 10:59
IDENTIFICATION OF PROTONATED PYRENE (1-C16 H11+ ) AND ITS NEUTRAL COUNTERPART ISOLATED IN
SOLID PARA-HYDROGEN
MOHAMMED BAHOU, Department of Applied Chemistry and Institute of Molecular Science, National
Chiao Tung University, Hsinchu 30010, Taiwan; YU-JONG WU, National Synchrotron Radiation Research
Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan; YUAN-PERN LEE, Department
of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010,
Taiwan and Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan.
RE09
15 min 11:16
VIBRONIC SPECTROSCOPY OF A STRUCTURAL ISOMER OF QUINOLINE: (Z)-PHENYLVINYLNITRILE
DEEPALI N. MEHTA-HURT, JOSEPH A. KORN, and TIMOTHY S. ZWIER, Department of Chemistry,
Purdue University, West Lafayette, IN 47907-2084 U.S.A..
RE10
15 min 11:33
HIGH RESOLUTION INFRARED SPECTRA OF PLASMA JET-COOLED DI- AND TRIACETYLENE IN THE C-H
STRETCH REGION BY CW CAVITY RING-DOWN SPECTROSCOPY
D. ZHAO, J. GUSS, A. WALSH, K. DONEY, H. LINNARTZ, Sackler Laboratory for Astrophysics, Leiden
Observatory, University of Leiden, P.O. Box 9513, NL-2300 RA Leiden, the Netherlands.
77
RF. ASTRONOMICAL SPECIES AND PROCESSES
THURSDAY, JUNE 20, 2013 – 1:30 PM
Chair: NICK INDRIOLO, Johns Hopkins University, Baltimore, MD
RF01
15 min 1:30
DISTRIBUTION OF SO2 AND SO IN THE ENVELOPE OF VY-CANIS MAJORIS: INSIGHT INTO CIRCUMSTELLAR SULFUR CHEMISTRY
Tucson, 85721; ,.
RF02
RADIO INTERFEROMETRIC DETECTION OF TiO AND TiO2 IN VY CANIS MAJORIS:
"SEEDS" OF INORGANIC DUST FORMATION
15 min 1:47
S. BRÜNKEN, H.S.P. MÜLLER, I. Physikalisches Institut, Universität zu Köln, 50937 Köln, Germany ; T.
KAMIŃSKI, K.M. MENTEN, Max-Planck Institut für Radioastronomie, 53121 Bonn, Germany; C.A. GOTTLIEB, N.A. PATEL, K.H. YOUNG, M.C. McCARTHY, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA 02138, USA; J.M. WINTERS, Institut de Radioastronomie Millimétrique, 38406 Saint-Martin
d’Héres, France; L. DECIN, Instituut voor Sterrenkunde, Katholieke Universiteit Leuven, 3001 Leuven, Belgium, and Sterrenkundig Instituut Anton Pannekoek, University of Amsterdam, 1098 Amsterdam, The Netherlands.
RF03
TRANSITION-METAL OXIDES IN WARM CIRCUMSTELLAR ENVIRONMENTS
15 min 2:04
MIROSŁAW R. SCHMIDT , N. Copernicus Astronomical Center, Department of Astrophysics, PL-87-100
Toruń, ul. Rabiańska 8, Poland ; TOMASZ KAMIŃSKI , Max Planck Institut für Radioastronomie, Auf
dem Hügel 69, 53121 Bonn, Germany ; and ROMUALD TYLENDA , N. Copernicus Astronomical Center,
Department of Astrophysics, PL-87-100 Toruń, ul. Rabiańska 8, Poland.
RF04
15 min 2:21
OBSERVATIONS AND ANALYSIS OF EXTENDED TAIL TOWARD RED IN THE DIFFUSE INTERSTELLAR
BANDS OF HERSCHEL 36
TAKESHI OKA, Department of Astronomy and Astrophysics, University of Chicago, Chicago, IL 60637;
DANIEL E. WELTY, SEAN JOHNSON, DONALD G.YORK, LEW M. HOBBS, Department of Physics and
Astronomy, Carthage College, Kenosha, WI 53140; and JULIE DAHLSTROM,.
RF05
15 min 2:38
MULTI-RESOLUTION STUDIES OF COMPLEX MOLECULES IN HIGH MASS STAR FORMING REGIONS
DOUGLAS N. FRIEDEL, Department of Astronomy, University of Illinois, 1002 W. Green St., Urbana, IL
61801.
RF06
15 min 2:55
IONIZATION OF H2 BY X-RAYS IN THE CENTRAL MOLECULAR ZONE OF THE GALACTIC CENTER
MASAHIRO NOTANI and TAKESHI OKA, Department of Astronomy and Astrophysics and Department of
Chemistry, the Enrico Fermi Institute, the University of Chicago, Chicago, Illinois, 60637, USA.
78
RF07
CARMA OBSERVATIONS OF PAH RICH SOURCES: NGC 2023, L134N AND GGD 27
15 min 3:12
P. BRANDON CARROLL, BRETT A. MCGUIRE, Department of Chemistry, California Institute of Technology, Pasadena CA, 91125; GEOFFREY A. BLAKE, Divisions of Geological and Planetary Sciences and
Chemistry and Chemical Engineering, California Institute of Technology, Pasadena CA, 91125.
RF08
15 min 3:29
A SEARCH FOR HCO AND HCN EMISSION IN PLANETARY NEBULAE
+
DEBORAH R. SCHMIDT, Department of Astronomy, Steward Observatory, The University of Arizona, Tucson, AZ 85721; and LUCY M. ZIURYS, Department of Chemistry and Biochemistry, Department of Astronomy, Steward Observatory, The University of Arizona, Tucson, AZ 85721.
Intermission
RF09
15 min 4:00
IDENTIFICATION AND ASSIGNMENT OF THE FIRST EXCITED TORSIONAL STATE OF CH2 DOH WITHIN THE
o2 , e2 , AND o3 TORSIONAL LEVELS
Oak Grove Dr., Pasadena, CA 91109, USA; L. H. COUDERT, LISA, CNRS/Universités Paris Est et Paris
Diderot, 61 Avenue du Général de Gaulle, 94010 Créteil, France; L. MARGULÈS, R. A. MOTIYENKO,
Laboratoire PhLAM, UMR 8523 CNRS, Bât. P5, Université des Sciences et Technologies de Lille 1, 59655
Villeneuve d’Ascq Cedex, France; and S. KLEE, Physikalisch-Chemisches Institut, Justus-Liebig-Universität
Gießen, 35392 Gießen, Germany.
RF10
15 min 4:17
ANALYSIS OF THE ROTATION-TORSION SPECTRUM OF CH2 DOH WITHIN THE e0 , e1 , AND o1 TORSIONAL
LEVELS
L. H. COUDERT, LISA, CNRS/Universités Paris Est et Paris Diderot, 61 Avenue du Général de Gaulle, 94010
Créteil, France; JOHN C. PEARSON, SHANSHAN YU, Jet Propulsion Laboratory, California Institute
of Technology, 4800 Oak Grove Dr., Pasadena, CA 91109, USA; L. MARGULÈS, R. A. MOTIYENKO,
RF11
15 min 4:34
A GLOBAL FIT OF THE X Π, A Σ , B Σ AND C Σ STATES OF SIX OH ISOTOPOLOGUES
2
2
+
2
+
2
+
SHANSHAN YU, JOHN C. PEARSON AND BRIAN J. DROUIN, Jet Propulsion Laboratory, California
Institute of Technology, Pasadena, CA 91109.
RF12
MICROWAVE SPECTROSCOPY OF TRANS-ETHYL METHYL ETHER IN THE GROUND STATE
15 min 4:51
KAORI KOBAYASHI, YUSUKE SAKAI, SHOZO TSUNEKAWA, Department of Physics, University of
Toyama, 3190 Gofuku, Toyama, 930-8555 Japan; TAIHEI MIYAMOTO, MASAHARU FUJITAKE and
NOBUKIMI OHASHI, Kanazawa University, Japan.
79
RF13
JET-COOLED EXCITATION SPECTRA OF LARGE BENZANNULATED
ANTHRACENYLMETHYL (C15 H11 ) and 1-PYRENYLMETHYL (C17 H11 )
BENZYL
15 min 5:08
RADICALS: 9-
GERARD D. O’CONNOR, GEORGE B. BACSKAY, GABRIELLE V.G. WOODHOUSE, TYLER P. TROY,
KLAAS NAUTA, SCOTT H. KABLE and TIMOTHY W. SCHMIDT, School of Chemistry, The University of
Sydney, NSW 2006, Australia.
RF14
ROTATIONAL STRUCTURE OF THE IR/FIR BANDS OF SMALL PAHS
15 min 5:25
O. PIRALIa , S. GRUETa , M. VERVLOET, Ligne AILES, Synchrotron SOLEIL, L’Orme des Merisiers SaintAubin, 91192 Gif sur Yvette Cedex - France; M. GOUBET, T. R. HUET, Laboratoire de Physique des Lasers,
Atomes et Molécules, UMR 8523 CNRS - Université Lille 1, Bâtiment P5, F-59655 Villeneuve d’Ascq Cedex,
France; R. GEORGES, Université de Rennes 1, Institut de Physique de Rennes, CNRS, UMR 6251, F-35042
Rennes Cedex, France; P. SOULARD, P. ASSELIN, UPMC Université Paris 06, UMR 7075 CNRS, Laboratoire de Dynamique, Interactions et Réactivité (LADIR), F-75005, Paris, France.
a Also
RF15
15 min 5:42
SYNCHROTRON-BASED HIGHEST RESOLUTION FTIR SPECTROSCOPY OF AZULENE, NAPHTHALENE
(C10 H8 ), INDOLE (C8 H6 N) AND BIPHENYL (C12 H10 )
S. ALBERT, M. QUACK, PHYSICAL CHEMISTRY, ETH ZÜRICH, CH-8093 ZÜRICH, SWITZERLAND;
PH. LERCH, SWISS LIGHT SOURCE, PAUL-SCHERRER-INSTITUTE, CH-5232 VILLIGEN, SWITZERLAND.
RF16
15 min 5:59
PHOTOGENERATION OF, AND EFFICIENT COLLISIONAL ENERGY TRANSFER FROM, VIBRATIONALLY EXCITED HYDROGEN ISOCYANIDE (HNC)
MICHAEL J. WILHELMa , Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104;
and HAI-LUNG DAI, Department of Chemistry, Temple University, Philadelphia, PA 19122.
a Present
Address: Department of Chemistry, Temple University, Philadelphia, PA 19122
80
RG. THEORY
Chair: SO HIRATA, University of Illinois, Urbana, IL
RG01
15 min 1:30
SYMMETRY, DEGENERACY, AND STATISTICAL WEIGHTS OF
H+
3
KYLE N. CRABTREE, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, 02138; BENJAMIN
J. McCALL, Departments of Chemistry, Astronomy, and Physics, University of Illinois, Urbana, IL, 61801.
RG02
15 min 1:47
INVESTIGATION OF LARGE-AMPLITUDE MOTIONS OF H+
5 AND THE DYNAMICS OF THE PROTON TRANSFER BETWEEN H+
3 and H2
ZHOU LIN and ANNE B. McCOY, Department of Chemistry and Biochemistry, The Ohio State University,
Columbus, OH 43210.
RG03
EINSTEIN A COEFFICIENTS FOR VIBRATION-ROTATIONAL TRANSITIONS OF NO
10 min 2:04
M. GUTIÉRREZ, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332,
USA; J. F. OGILVIE, Escuela de Química and CELEQ, Universidad de Costa Rica, San José 2060, Costa Rica.
RG04
15 min 2:16
OZONE PHOTOLYSIS: STRONG ISOTOPOLOGUE/ISOTOPOMER SELECTIVITY IN THE STRATOSPHERE
FABIEN GATTI, CTMM Institut Charles Gerhardt UMR-CNRS 5253 University of Montpellier, France;
STEVE NDENGUE, REMY JOST, Univ. Grenoble 1 / CNRS, LIPhy UMR 5588, Grenoble, F-38041, France;
GABOR HALASZ, AGNES VIBOK, Department of Information Technology, University of Debrecen, P.O.
Box 12, H-4010 Debrecen, Hungary.
RG05
15 min 2:33
LINE SHAPE PARAMETERS FOR CO2 TRANSITIONS: ACCURATE PREDICTIONS FROM COMPLEX ROBERTBONAMY CALCULATIONS
JULIEN LAMOUROUX AND ROBERT R. GAMACHE, Department of Environmental, Earth, and Atmospheric Sciences, University of Massachusetts Lowell, Lowell, MA 01854, USA.
RG06
15 min 2:50
AB INITIO CLASSICAL DYNAMICS SIMULATIONS OF CO2 LINE-MIXING EFFECTS IN INFRARED BANDS
JULIEN LAMOUROUXa , JEAN-MICHEL HARTMANN, HA TRAN, Laboratoire Interuniversitaire des
Systèmes Atmosphériques (LISA, CNRS UMR 7583),Université Paris-Est Créteil, Université Paris Diderot,
Institut Pierre-Simon Laplace, 94010 Créteil Cedex, France; MARCEL SNELS, ISAC-CNR, Via del Fosso
del Cavaliere, 100 00133 Rome, Italy; STEFANIA STEFANI and GIUSEPPE PICCIONI, IAPS-IASF, Via del
Fosso del Cavaliere, 100 00133 Rome, Italy.
a Support
by the French Agence Nationale de la Recherche (ANR) is gratefully acknowledged.
81
RG07
TOWARDS EXPERIMENTAL ACCURACY FROM THE FIRST PRINCIPLES
15 min 3:07
O.L. POLYANSKY, L. LODI, J. TENNYSON, Department of Physics and Astronomy, University College
London, Gower Street, London WC1E 6BT, UK; N.F. ZOBOV, Institute of Applied Physics, Russian Academy
of Sciences, 46 Uljanova St., 603950, Nizhny Novgorod, Russia.
RG08
15 min 3:24
HOW MANY VIBRATIONAL LEVELS DOES THE GROUND ELECTRONIC STATE OF THE SODIUM DIMER
SUPPORT?
Cyprus.
Intermission
RG09
15 min 4:00
RESONANCE AND REVIVALS IN QUANTUM ROTORS: COMPARING HALF-INTEGER SPIN AND INTEGER
SPIN
ALVASON ZHENHUA LI, and WILLIAM G. HARTER, Microelectronics-Photonics Program, Department
of Physics, University of Arkansas, Fayetteville, AR 72701.
RG10
15 min 4:17
EFFECTS OF SUPERFINE STRUCTURE LEVEL-CLUSTER CROSSING ON AMPLITUDE AND PHASE REVIVAL
DYNAMICS: COMPARING TETRAHEDRAL AND OCTAHEDRAL SPHERICAL ROTORS WITH ICOSAHEDRAL
ROTORS
WILLIAM G. HARTER, and ALVASON ZHENHUA LI, Department of Physics, University of Arkansas,
Fayetteville, AR 72701.
RG11
EXACT QUANTUM DYNAMICS CALCULATIONS USING PHASE SPACE WAVELETS
15 min 4:34
THOMAS HALVERSON, BILL POIRIER, Department of Chemistry and Biochemistry, and Department of
Physics, Texas Tech University, P.O. Box 41061, Lubbock TX, USA.
RG12
15 min 4:51
ACHIEVING THE COMPLETE-BASIS LIMIT IN LARGE MOLECULAR CLUSTERS: COMPUTATIONALLY EFFICIENT PROCEDURES TO ELIMINATE BASIS-SET SUPERPOSITION ERROR
RYAN M. RICHARD, JOHN M. HERBERT, Department of Chemistry and Biochemistry, The Ohio State
RG13
15 min 5:08
VIBRATIONAL ANYLASIS ON I(H2 O) and I(D2 O) SPECTRA
−
−
MENG HUANG and ANNE B. McCOY, Department of Chemistry, The Ohio State University, Columbus,
Ohio 43210.
RG14
AB-INITIO STUDY OF THE GROUP 2 HYDRIDE ANIONS
10 min 5:25
JOE P. HARRIS, TIMOTHY G. WRIGHT and DANIEL R. MANSHIP, School of Chemistry, University Park,
University of Nottingham, NG7 2RD, United Kingdom.
82
RG15
15 min 5:37
ACCURATE INTERMOLECULAR INTERACTIONS AT DRAMATICALLY REDUCED COST AND A MANY-BODY
ENERGY DECOMPOSITION SCHEME FOR XPol+SAPT
KA UN LAO and JOHN M. HERBERT, Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH 43210.
83
RH. DYNAMICS
Chair: GEOFFREY DUXBURY, University of Strathclyde, Bearsden, United Kingdom
RH01
15 min 1:30
TORSION-INVERSION TUNNELING PATTERNS IN THE CH-STRETCH VIBRATIONALLY EXCITED STATES OF
THE G12 MOLECULES
MAHESH B. DAWADI, RAM S. BHATTA and DAVID S. PERRY, Department of Chemistry, The University
of Akron, Akron OH, 44325.
RH02
15 min 1:47
COUPLING OF THE C-H STRETCH TO LARGE-AMPLITUDE TORSION AND INVERSION MOTIONS: COMPARISON OF CH3 CH2 . , CH3 OH2 + AND CH3 NH2
RAM S. BHATTA, Department of Polymer Science and Department of Chemistry, The University of Akron;
DAVID S. PERRY, Department of Chemistry, The University of Akron, OH 44325.
RH03
15 min 2:04
HYDROGEN ABSTRACTION FROM METHANE BY BROMINE AND CHLORINE RADICALS: A DYNAMICS
COMPARISON
ANDREW E. BERKE, ETHAN H. VOLPA, F. FLEMING CRIM, Chemistry Department, University of Wisconsin - Madison, Madison, Wisconsin 53706.
RH04
A NEW APPROACH TOWARD TRANSITION STATE SPECTROSCOPY
15 min 2:21
KIRILL PROZUMENT, RACHEL G. SHAVER, MONIKA A. CIUBA, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139; JOHN S. MUENTER, Department of Chemistry,
University of Rochester, Rochester, NY 14627; G. BARRATT PARK, Department of Chemistry, Massachusetts
Institute of Technology, Cambridge, MA 02139; JOHN F. STANTON, Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, TX 78712; HUA GUO, Department of Chemistry, University
of New Mexico, Albuquerque, NM 87131; BRYAN M. WONG, Materials Chemistry Department, Sandia National Laboratories, Livermore, CA 94550; DAVID S. PERRY, Department of Chemistry, The University of
Akron, Akron, OH 44325; ROBERT W. FIELD, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139.
RH05
15 min 2:38
PHOTODISSOCIATION DYNAMICS OF VINYL CYANIDE STUDIED BY CHIRPED-PULSE MILLIMETER-WAVE
SPECTROSCOPY OF HCN AND HNC PRODUCTS
KIRILL PROZUMENT, RACHEL G. SHAVER, JOSHUA H. BARABAN, G. BARRATT PARK, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139; ARTHUR G. SUITS, Department of Chemistry, Wayne State University, Detroit, MI 48202; JOHN S. MUENTER, Department of
Chemistry, University of Rochester, Rochester, NY 14627; ROBERT W. FIELD, Department of Chemistry,
Massachusetts Institute of Technology, Cambridge, MA 02139.
84
RH06
15 min 2:55
ENERGY TRANSFER AND LASING OF THE LOWER Ar(3p 4p) STATES IN Ar and He
5
JIANDE HAN and MICHAEL C. HEAVEN, Department of Chemistry, Emory University, Atlanta, GA 30322.
RH07
GRAVITATON WAVE AND GRAVITATIONAL-PHOTON INTERACTION
15 min 3:12
KHOLMURAD KHASANOV, Lomonosov Moscow State University, Gas and Wave Dynamics Department,
Moscow, Russia, 119991, GSP-1, 1 Leninskie Gory Str.Email: [email protected].
Intermission
RH08
15 min 3:45
PROBING CHEMICAL DYNAMICS WITH HIGH RESOLUTION SPECTROSCOPY: CHIRPED-PULSE FOURIERTRANSFORM MICROWAVE SPECTROSCOPY COUPLED WITH A HYPERTHERMAL SOURCE
NATHANAEL M. KIDWELL,
VANESA
VAQUERO
VARA
,
DEEPALI
N.
MEHTAHURT, JOSEPH A. KORN, BRIAN C. DIAN, and TIMOTHY S. ZWIER, Department of Chemistry,
Purdue University, West Lafayette, IN 47907-2084.
RH09
15 min 4:02
J-SPECIFIC DYNAMICS IN AN OPTICAL CENTRIFUGE USING TRANSIENT IR SPECTROSCOPY
MATTHEW J. MURRAY, QINGNAN LIU, CARLOS TORO and AMY S. MULLIN, Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742.
RH10
15 min 4:19
OBSERVATION OF NEW DYNAMICS IN THE STATE-RESOLVED COLLISIONAL RELAXATION OF HIGHLY
EXCITED MOLECULES
GERALDINE O. ECHEBIRI, MATTHEW SMARTE, WENDELL W. WALTERS, JILL M. CLEVELAND,
CHRISTINE MCCARL, ALICE KUNIN and AMY S. MULLIN, Department of Chemistry and Biochemistry,
University of Maryland, College Park, MD 20742.
RH11
10 min 4:36
TIME RESOLVED INFRARED EMISSION FROM VIBRATIONAL EXCITED ACETYLENE FOLLOWING SUPER
ENERGY TRANSFER COLLISIONS WITH HOT HYDROGEN
J. M. SMITH, M. NIKOW, J. MA AND H.L. DAI, Department of Chemistry, Temple University, Philadelphia,
Pennsylvania 19122, USA.
RH12
15 min 4:48
TIME-RESOLVED IR-IR DOUBLE RESONANCE FOR THE ν4 and 2ν4 −ν4 VIBRATION-ROTATION TRANSITIONS
OF CH3 F
YUSUKE OKABAYASHI, JIAN TANG, YUKI MIYAMOTO, KENTAROU KAWAGUCHI, Graduate
School of Natural Science and Technology, Okayama University, 3-1-1 Tsushima-Naka, Okayama 700-8530,
Japan.
85
RH13
VIBRATIONAL ENERGY RELAXATION OF CHOLOROIODOMETHANE IN COLD ARGON
15 min 5:05
AMBER JAIN and EDWIN L. SIBERT III, Department of Chemistry and Theoretical Chemistry Institute,
University of Wisconsin-Madison, WI 53706.
RH14
15 min 5:22
DETERMINATION OF DIFFERENTIAL CROSS SECTIONS OF THE STATE-TO-STATE INELASTIC COLLISIONS
IN BULBS. A THREE-DIMENSIONAL SLICED FLUORESCENCE IMAGING STUDY
KUO-MEI CHEN, Department of Chemistry, National Sun Yat-sen University, Kaohsiung, Taiwan, Republic
of China.
RH15
ION IMAGING STUDIES OF CH2 I2 PHOTODISSOCIATION AT 248 NM
15 min 5:39
JULIA H. LEHMAN, HONGWEI LI and MARSHA I. LESTER, Department of Chemsitry, University of
Pennsylvania, Philadelphia, PA 19104-6323.
86
RI. ATMOSPHERIC SPECIES
Chair: YEN-CHU HSU, Academia Sinica, Taipei, Taiwan
RI01
HITRAN2012: DOWN TO EARTH
15 min 1:30
RI02
15 min 1:47
CAVITY-ENHANCED, FREQUENCY-AGILE RAPID SCANNING (FARS) SPECTROSCOPY: MEASUREMENT
PRINCIPLES
JOSEPH T. HODGES, DAVID A. LONG, GAR-WING TRUONG, KEVIN O. DOUGLASS, STEPHEN E.
MAXWELL, ROGER VAN ZEE, and DAVID F. PLUSQUELLIC, National Institute of Standards and Technology, 100 Bureau Drive, Gaithersburg, MD 20899, USA.
RI03
15 min 2:04
CAVITY-ENHANCED, FREQUENCY-AGILE RAPID SCANNING (FARS) SPECTROSCOPY: EXPERIMENTAL REALIZATIONS AND MEASUREMENT RESULTS
DAVID A. LONG, GAR-WING TRUONG, ROGER VAN ZEE, DAVID F. PLUSQUELLIC, and JOSEPH T.
HODGES, National Institute of Standards and Technology, 100 Bureau Drive, Gaithersburg, MD 20899, USA.
RI04
15 min 2:21
PERFORMANCE OF A CRYOGENIC 21 METER-PATH COPPER HERRIOTT CELL VACUUM COUPLED TO A
BRUKER 125HR SYSTEM
ARLAN W. MANTZ, Dept. of Physics, Connecticut College, New London, CT 06320; KEEYOON SUNG,
TIMOTHY J. CRAWFORD, SHANSHAN YU, LINDA R. BROWN, Jet Propulsion Laboratory, California
Institute of Technology, 4800 Oak Grove Dr.,Pasadena, CA 91109; MARY ANN H. SMITH, Science Directorate, NASA Langley Research Center, Hampton, VA 23681; V. MALATHY DEVI, D. CHRIS BENNER,
Dept. of Physics, The College of William and Mary, Williamsburg, VA 23187.
RI05
15 min 2:38
FREQUENCY-COMB REFERENCED, SUB-DOPPLER SPECTROSCOPY OF HOT BANDS OF ACETYLENE IN
THE REGION OF THE ν1 + ν3 COMBINATION BAND
CHRISTOPHER P. MCRAVEN, Chemistry Department, Brookhaven National Laboratory, Upton, New York
11973; MATTHEW J. CICH, SALVATORE M. CAIOLA, Department of Chemistry, Stony Brook University,
Stony Brook, New York 11794; TREVOR J. SEARSa , Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973; GREGORY E. HALL, Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973.
a also:
Department of Chemistry, Stony Brook University, Stony Brook, New York 11794
87
RI06
15 min 2:55
DIAGNOSTIC CHEMICAL ANALYSIS OF EXHALED HUMAN BREATH USING A NOVEL SUBMILLIMETER/TERAHERTZ SPECTROSCOPIC APPROACH
ALYSSA M. FOSNIGHT, BENJAMIN L. MORAN, DANIELA R. BRANCO, JESSICA R. THOMAS, IVAN
R. MEDVEDEV, Department of Physics, Wright State University, 3640 Colonel Glenn Highway, Dayton, OH
45435, USA.
RI07
15 min 3:12
TERAHERTZ CHEMICAL ANALYSIS OF EXHALED HUMAN BREATH - BROAD ESSAY OF CHEMICALS
DANIELA R. BRANCO, ALYSSA M. FOSNIGHT, JESSICA R. THOMAS, IVAN R. MEDVEDEV, Department of Physics, Wright State University, 3640 Colonel Glenn Highway, Dayton, OH 45435, USA.
Intermission
RI08
SF6 : THE FORBIDDEN BAND UNVEILED
15 min 3:45
V. BOUDON, Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS–Université de Bourgogne, 9 Av. A. Savary, BP 47870, F-21078 Dijon Cedex, France; L. MANCERON, Laboratoire de Dynamique, Interactions et Réactivité, CNRS UMR 7075, 4 Place Jussieu, F-75252 Paris Cedex, France; F.
KWABIA-TCHANA, Laboratoire Interuniversitaire des Systèmes Atmosphériques, UMR CNRS 7583, Université Paris-Est Créteil et Université Paris-Diderot, 61 Avenue du Général de Gaulle, 94010 Créteil Cedex,
France; P. ROY, Ligne AILES – Synchrotron SOLEIL, L’Orme des Merisiers, F-91192 Gif-sur-Yvette, France.
RI09
15 min 4:02
FREQUENCY ANALYSIS OF THE 10 µm REGION OF THE ETHYLENE SPECTRUM USING THE D2h TOP DATA
SYSTEM.
M.-T. BOURGEOIS, M. ROTGER, Groupe de Spectrométrie Moléculaire et Atmosphérique, CNRS UMR
7331, Université de Reims Champagne-Ardenne, Moulin de la Housse, B.P. 1039, Cases 16-17, F-51687 Reims
Cedex, France; M. TUDORIE, J. VANDER AUWERA, Service de Chimie Quantique et Photophysique, C.P.
160/09, Université Libre de Bruxelles, 50, avenue F. D. Roosevelt, B-1050 Brussels, Belgium; V. BOUDON,
Laboratoire Interdisciplinaire Carnot de Bourgogne, CNRS UMR 6303, Université de Bourgogne, 9, Avenue
Alain Savary, BP 47870, F-21078 Dijon Cedex, France.
RI10
15 min 4:19
INFRARED ABSORPTION SPECTRUM OF THE SIMPLEST CRIEGEE INTERMEDIATE CH2 OO
YU-TE SU, YU-HSUAN HUANG, HENRYK WITEK, Department of Applied Chemistry and Institute of
Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan; YUAN-PERN LEE, Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu
30010, Taiwan and Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan.
RI11
15 min 4:36
POSSIBLE OBSERVATION OF THE A - A ELECTRONIC TRANSITION OF THE METHYLENE PEROXY
CRIEGEE INTERMEDIATE
3
′
1
′
NEAL D. KLINE and TERRY A. MILLER, Laser Spectroscopy Facility, Department of Chemistry, The Ohio
State University, 120 W. 18th Avenue, Columbus, Ohio 43210; MARC COONS and JOHN HERBERT, Department of Chemistry, The Ohio State University, Columbus, Ohio 43210.
88
RI12
15 min 4:53
UV SPECTRUM AND PHOTOCHEMISTRY OF THE SIMPLEST CRIEGEE INTERMEDIATE CH2 OO
JOSEPH M. BEAMES, FANG LIU, LU LU, and MARSHA I. LESTER, Department of Chemsitry, University
of Pennsylvania, Philadelphia, PA 19104-6323.
RI13
15 min 5:10
SPECTROSCOPIC CHARACTERIZATION OF AN ALKYL-SUBSTITUTED CRIEGEE INTERMEDIATE CH3 CHOO
AND ITS OH RADICAL PRODUCTS
JOSEPH M. BEAMES, FANG LIU, LU LU and MARSHA I. LESTER, Department of Chemsitry, University
RI14
15 min 5:27
RATE CONSTANTS AND DEUTERIUM KINETIC ISOTOPE EFFECTS FOR METHOXY RADICAL REACTING
WITH NO2 AND O2
J. CHAI, H. HU, T. S. DIBBLE, Department of Chemistry, College of Environmental Science and Forestry,
State University of New York, Syracuse, New York 13210; G. S. TYNDALL, J. J. ORLANDO, Atmospheric
Chemistry Division, National Center for Atmospheric Research, Boulder, Colorado 80305.
RI15
15 min 5:44
ABSOLUTE VUV PHOTOIONIZATION SPECTRA FOR HCHO, HO2 , AND H2 O2 FROM 10.5-12.0 eV
LEAH G. DODSONa , LINHAN SHEN, NATHAN C. EDDINGSAASb , KANA TAKEMATSU, California
Institute of Technology, Division of Chemistry and Chemical Engineering, Pasadena, CA; JOHN D. SAVEE,
OLIVER WELZ, CRAIG A. TAATJES, DAVID L. OSBORN, Sandia National Lab, Livermore, CA; STANLEY P. SANDER, Jet Propulsion Laboratory, Pasadena, CA; MITCHIO OKUMURA, California Institute of
Technology, Division of Chemistry and Chemical Engineering, Pasadena, CA.
a Support
b Present
from the EPA STAR fellowship and NSF grant CHE-095749 are gratefully acknowledged
address: Rochester Institute of Technology, Rochester, NY
RI16
LABORATORY INVESTIGATION OF THE AIRGLOW BANDS
15 min 6:01
BRIAN DROUIN, SHANSHAN YU, TIMOTHY J. CRAWFORD, CHARLES E. MILLER, Jet Propulsion
Laboratory, California Institute of Technology, 4800 Oak Grove Dr., Pasadena, CA 91109; JENG-HWA YEE,
Applied Physics Laboratory, The Johns Hopkins University, 111000, Johns Hopkins Rd, Laurel, MD 207236099.
89
RJ. INFRARED/RAMAN
Chair: LAURA MCCUNN, Marshall University, Huntington, WV
RJ01
15 min 1:30
EXPERIMENTAL FT-IR, DISPERSIVE RAMAN AND THEORETICAL DFT CALCULATIONS ON CU(II) CHLORIDE COMPLEX OF P-TOLUIDINE
TAYYIBE BARDAKCI, MUSTAFA KUMRU, Department of Physics, Faculty of Arts and Sciences, Fatih
University, 34500 Buyukcekmece, Istanbul, Turkey.
RJ02
15 min 1:47
INFRARED SPECTROSCOPY OF PHENOL-TRIETHYLSILANE DIHYDROGEN-BONDED CLUSTER
HARUKI ISHIKAWA, TAKAYUKI KAWASAKI, Department of Chemistry, School of Science, Kitasato University, Minami-ku, Sagamihara 252-0373, Japan.
RJ03
10 min 2:04
A NEW, LOW TEMPERATURE LONG PATH CELL FOR MID-IR to THz SPECTROSCOPY WITH SYNCHROTRON
RADIATION AT SOLEIL
F. KWABIA TCHANA, F. WILLAERT, X. LANDSHEERE, J.M. FLAUD, Laboratoire Interuniversitaire
des Systémes Atmosphériques (LISA), UMR CNRS 7583, Université Paris-Est Créteil (UPEC) et Université
Paris-Diderot (UPD), 61 Avenue du Général de Gaulle, 94010 Créteil Cedex, France; L. LAGO, M. CHAPUIS, P. ROY„ Synchrotron SOLEIL, L’Orme des Merisiers Saint-Aubin, 91192 Gif-sur-Yvette, France;
L. MANCERON, Laboratoire LADIR, UMR7075 CNRS, Université Pierre et Marie Curie, 75252 Paris Cedex,
France.
RJ04
10 min 2:16
SYNCHROTRON BASED HIGH RESOLUTION FAR-IR SPECTROSCOPY OF 1,1-DICHLOROETHYLENE
REBECCA A. PEEBLES, LENA F. ELMUTI, and SEAN A. PEEBLES, Department of Chemistry, Eastern
Illinois University, 600 Lincoln Ave., Charleston, IL 61920; DANIEL A. OBENCHAIN, Department of Chemistry, Wesleyan University, 52 Lawn Avenue, Middletown, CT 06459-0180.
RJ05
15 min 2:28
SYNCHROTRON-BASED STUDY OF THE FAR IR SPECTRUM OF SILACYCLOBUTANE: THE ν29 AND ν30
BANDS
ZIQIU CHEN, CODY W. VAN DIJK, SAMANTHA HARDER AND JENNIFER VAN WIJNGAARDEN,
Department of Chemistry, University of Manitoba, Winnipeg MB R3T 2N2 Canada.
RJ06
15 min 2:45
GAS PHASE VIBRATIONAL SPECTROSCOPY OF WEAKLY VOLATIL SAFE TAGGANTS USING A SYNCHROTRON SOURCE
ARNAUD CUISSET, FRANCIS HINDLE, GAEL MOURET, Laboratoire de Physico-Chimie de
l’Atmosphère, 189A Ave. Maurice Schumann, 59140 Dunkerque, France; SEBASTIEN GRUET, OLIVIER
PIRALI, PASCALE ROY, Ligne AILES, synchrotron SOLEIL, L’Orme des Merisiers, Saint Aubin, BP 48,
91192 Gif-sur-Yvette, France..
90
RJ07
15 min 3:02
SYNCHROTRON BASED FOURIER TRANSFORM FAR-INFRARED SPECTROSCOPY OF CH3NO2
SYLVESTRE TWAGIRAYEZU, BRANT E. BILLINGHURST AND TIM MAY , Canadian Light Source
Inc., University of Saskatchewan, 44 Innovation Blvd, Saskatoon, SK S7N 2V3; MAHESH B. DAWADI,
DAVID S. PERRY, Department of Chemistry, The University of Akron, Akron OH 44325.
Intermission
RJ08
15 min 3:40
ISOLATION AND CHARACTERIZATION OF FORMATE/NI(CYCLAM)
VIBRATIONAL PREDISSOCIATION
2+
COMPLEXES WITH CRYOGENIC ION
ARRON B. WOLK, JOSEPH A. FOURNIER , CONRAD T. WOLKE, and MARK A. JOHNSON, DEPARTMENT OF CHEMISTRY, YALE UNIVERSITY, NEW HAVEN, CT 06520.
RJ09
15 min 3:57
CHARACTERIZATION OF STRUCTURAL MOTIFS FOR CO2 ACCOMMODATION BY IONIC SPECIES RELEVANT TO PHOTOELECTROCATALYSIS USING CRYOGENIC VIBRATIONAL PREDISSOCIATION SPECTROSCOPY
JOSEPH A. FOURNIER, CHRISTOPHER J. JOHNSON, CONRAD T. WOLKE, ARRON B. WOLK,
CHRISTOPHER M. LEAVITT, KRISTEN J. BREEN, and MARK A. JOHNSON, DEPARTMENT OF
CHEMISTRY, YALE UNIVERSITY, NEW HAVEN, CT 06520.
RJ10
Post-deadline Abstract - Original Abstract Withdrawn
15 min 4:14
THZ SPECTROSCOPY AND DFT MODELING OF INTERMOLECULAR VIBRATIONS IN HYDROPHOBIC
AMINO ACIDS
MICHAEL R. C. WILLIAMS, DANIEL J. ASCHAFFENBURG, CHARLES A. SCHMUTTENMAER, Yale
University, Department of Chemistry, P.O. Box 208107, 225 Prospect St., New Haven, CT 06520-8107, USA..
RJ11
15 min 4:31
STRUCTURES AND THE HYDROGEN BONDING ABILITIES OF ESTROGENS STUDIED BY SUPERSONIC
JET/LASER SPECTROSCOPY
FUMIYA MORISHIMA, YOSHIYA INOKUCHI and TAKAYUKI EBATA, Graduate School of Science, Hiroshima University 1-3-1, Kagamiyama, Higashi-Hiroshima 739-8526, JAPAN.
RJ12
15 min 4:48
DEUTERATION EFFECT ON THE NH/ND STRETCH BAND OF THE JET-COOLED 7-AZAINDOLE AND ITS TAUTOMERIC DIMERS: RELATION TO THE GROUND-STATE DOUBLE PROTON-TRANSFER REACTION
HARUKI ISHIKAWA, Department of Chemistry, School of Science, Kitasato University,
Minami-ku, Sagamihara 252-0373, Japan; TAKUMI NAKANO, TSUKIKO TAKASHIMA, HIROKI YABUGUCHI, and KIYOKAZU FUKE, Department of Chemistry, Graduate School of Scinec,
Kobe University, Nada-ku, Kobe 657-8501, Japan.
RJ13
10 min 5:05
SOLVENT EFFECTS ON IR MODES OF (R)-3-METHYLCYCLOPENTANONE CONFORMERS: A COMPUTATIONAL INVESTIGATION
WATHEQ AL-BASHEER, Physics Department, King Fahd University of Petroleum and Minerals, Dhahran
31261 Saudi Arabia.
91
RJ14
CHIRAL RECOGNITION IN NEUTRAL AND IONIC MOLECULAR COMPLEXES
15 min 5:17
ANANYA SEN, AUDE BOUCHET, VALERIA LEPERE, KATIA LE BARBU-DEBUS, and ANNE
ZEHNACKER-RENTIEN, CNRS, Institut des Sciences Moléculaires d’Orsay (ISMO), UMR 8214, Orsay
F-91405, and Univ. Paris-Sud, Orsay F-91405, France.
92
RK. MICROWAVE
Chair: SUSANNA WIDICUS WEAVER, Emory University, Atlanta, GA
RK01
10 min 1:30
SPECTROSCOPY OF THE GROUND, FIRST AND SECOND EXCITED TORSIONAL STATES OF ACETALDEHYDE FROM 0.05 TO 1.6 THz.
VADIM V. ILYUSHINa , IVAN SMIRNOV, EUGENE A. ALEKSEEV, Institute of Radio Astronomy of NASU,
Chervonopraporna 4, 61002 Kharkov, Ukraine; LAURENT MARGULÈSb , ROMAN A. MOTIYENKO, Laboratoire de Physique des Lasers, Atomes et Molècules, UMR 8523 CNRS-Universitè Lille 1, Bâtiment P5,
F-59655 Villeneuve d’Ascq Cedex, France; BRIAN DROUIN, Jet Propulsion Laboratory, California Institute
of Technology, 4800 Oak Grove Drive, Pasadena, CA 91109-8099, USA.
a Part
b This
of this work was done within the Ukrainian-French CNRS-PICS 6051 project.
work was supported by the CNES and the Action sur Projets de l’INSU, PCMI.
RK02
15 min 1:42
A SEMIEXPERIMENTAL EQUILIBRIUM STRUCTURE OF cis-HEXATRIENE FROM MICROWAVE SPECTROSCOPY
NORMAN C. CRAIG, YIHUI CHEN, HANNAH A. FUSON, HENGFENG TIAN, and HERMAN VAN BESIEN, Department of Chemistry and Biochemistry, Oberlin College, Oberlin, Ohio 44074; H. D. RUDOLPH,
Department of Chemistry, University of Ulm, D-89069 Ulm, Germany; JEAN DEMAISON, Laboratoire de
Physique des Lasers, Atomes et Molécules, Université de Lille I, 59655 Villeneuve d’Ascq Cedex, France.
RK03
15 min 1:59
ANALYSIS OF THE ROTATIONAL STRUCTURE IN THE HIGH-RESOLUTION INFRARED SPECTRA OF cis, cisAND trans, trans-1,4-DIFLUOROBUTADIENE-1-d1 AND trans, trans-1,4-DIFLUOROBUTADIENE-1,4-d2
NORMAN C. CRAIG, YIHUI CHEN, YUHUA LU, CHRISTOPHER F. NEESE, and DEACON J. NEMCHICK, Department of Chemistry and Biochemistry, Oberlin College, Oberlin, OH 44074; THOMAS A.
BLAKE, Pacific Northwest National Laboratory, Richland, WA 99352.
RK04
THE DELICATE BALANCE OF HYDROGEN BOND FORCES IN D-THREONINOL
10 min 2:16
DI ZHANG, VANESA VAQUERO VARA, BRIAN C. DIAN and TIMOTHY S. ZWIER, Department of
Chemistry, Purdue University, West Lafayette, IN 47907; DAVID W. PRATT, Department of Chemistry, University of Vermont, Burlington VT 05405.
RK05
WAVEGUIDE CHIRPED-PULSE
ETHOXYETHANOL
FOURIER
TRANSFORM
MICROWAVE
10 min 2:28
SPECTROSCOPY OF 2-
MARIA A. PHILLIPS and STEVEN T. SHIPMAN, Division of Natural Sciences, New College of Florida,
Sarasota, FL 34243.
93
RK06
10 min 2:40
WAVEGUIDE CHIRPED-PULSE FOURIER TRANSFORM MICROWAVE SPECTROSCOPY OF 1-PROPANETHIOL
BRITTANY P. GORDON and STEVEN T. SHIPMAN, Division of Natural Sciences, New College of Florida,
Sarasota, FL 34243.
RK07
15 min 2:52
ENERGY TRANSFER COLLISIONAL PROCESS INVOLVING HETEROMOLECULAR COLLISIONS BETWEEN
METHYL FLUORIDE AND N2 , Ar, He, CO2 , AND AIR
DANE J. PHILLIPS, IERUS Technologies, 2904 Westcorp Blvd Ste 210, Huntsville, AL 35805;
HENRY O. EVERITT, Army Aviation and Missile RD&E Center, Redstone Arsenal, AL 35898.
RK08
MILLIMETER WAVE TUNNELING-ROTATIONAL SPECTRUM OF PHENOL
15 min 3:09
L. KOLESNIKOVÁ, A. M. DALY, J. L. ALONSO, Grupo de Espectroscopía Molecular (GEM), Edificio
47011 Valladolid, Spain; B. TERCERO, J. CERNICHARO, Departamento de Astrofísica, Centro de Astrobiología CAB, CSIC-INTA, Ctra. de Torrejón a Ajalvir km 4, 28850 Madrid, Spain.
Intermission
RK09
ROTATIONAL SPECTROSCOPY UNVEILS ELEVEN CONFORMERS OF ADRENALINE
15 min 3:40
C. CABEZAS, V. CORTIJO, S. MATA, J. C. LÓPEZ, J. L. ALONSO, Grupo de Espectroscopía Molecular
RK10
PROBING THE TAUTOMERISM OF HISTIDINE
10 min 3:57
C. BERMÚDEZ, C. CABEZAS, S. MATA, J. L. ALONSO, Grupo de Espectroscopía Molecular (GEM),
RK11
15 min 4:09
DEUTERIUM QUADRUPOLE COUPLING IN PROPIOLIC ACID AND FLUOROBENZENES MEASURED WITH
FTMW SPECTROMETER USING MULTIPLE FIDS a
MING SUN, BRYAN M. SARGUS, SPENCER J. CAREY and STEPHEN G. KUKOLICH, Department of
Chemistry and Biochemistry, The University of Arizona, Tucson, Arizona 85721..
a Supported
RK12
MICROWAVE SPECTRA OF FLUORINATED PROPIONIC ACIDS AND THEIR HYDRATES
15 min 4:26
DANIEL A. OBENCHAIN, G. S. GRUBBS II, STEWART E. NOVICK, Department of Chemistry, Wesleyan
University, Middletown, CT 06459; STEPHEN A. COOKE, School of Natural and Social Sciences, Purchase
College, SUNY, 735 Anderson Hill Road, Purchase, NY 10577; AGAPITO SERRATO III and WEI LIN, Department of Chemistry and Environmental Science, University of Texas at Brownsville, Brownsville, TX 78520.
94
RK13
MW SPECTROSCOPY COUPLED WITH ULTRAFAST UV LASER VAPORIZATION:
SUCCINIC ACID IN THE GAS PHASE
10 min 4:43
ESTIBALIZ MENDEZ, PATRICIA ECIJA, EMILIO J. COCINERO, FERNANDO CASTANO, FRANCISCO J. BASTERRETXEA, Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Ap.644, E-48940, Bilbao, Spain; PETER D. GODFREY, DON MCNAUGHTON, School of Chemistry, Box 23 Victoria 3800 Monash University, Australia; MICHAELA K.
JAHN, K.P. RAJAPPAN NAIR, JENS-UWE GRABOW, Institut für Physikalische Chemie und Elektrochemie,
Gottfried-Wilhelm-Leibniz-Universität, 30167 Hannover, Germany.
RK14
15 min 4:55
CHIRPED-PULSE FOURIER TRANSFORM MICROWAVE SPECTROSCOPY OF 3-VINYLBENZALDEHYDE
MIRANDA SMITH and GORDON G. BROWN, Department of Science and Mathematics, Coker College,
300 E College Ave., Hartsville, SC 29550..
RK15
CHIRPED-PULSE
FOURIER
CHLOROBENZALDEHYDE
TRANSFORM
MICROWAVE
SPECTROSCOPY
10 min 5:12
OF
M ET A-
SEAN T. ARNOLD, JESSICA A. GARRETT, and GORDON G. BROWN, Department of Science and Mathematics, Coker College, 300 E College Ave., Hartsville, SC 29550..
RK16
15 min 5:24
ROTATIONAL SPECTRUM OF HEXAFLUOROISOPROPANOL AND COMAPRISION TO HEXAFLUOROISOBUTENE
ABHISHEK SHAHI, and E. ARUNAN, Department of Inorganic and Physical Chemistry, Indian Institute of
Science, Bangalore, India-560012.
95
FA. ASTRONOMICAL SPECIES AND PROCESSES
FRIDAY, JUNE 21, 2013 – 8:30 AM
Chair: KYLE CRABTREE, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA
FA01
15 min 8:30
THE PUBLICLY AVAILABLE PREBIOTIC INTERSTELLAR MOLECULAR SURVEY (PRIMOS):
EXPANDING SPECTROSCOPIC CHARACTERIZATIONS, EXTENDING TO NEW SOURCES, AND ADDING TO
THE KNOWN MOLECULAR INVENTORY
BRETT A. McGUIRE, P. BRANDON CARROLL, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125; JOANNA F. CORBY, Department of Astronomy, University
of Virginia, Charlottesville, VA 22904; RYAN A. LOOMIS, Department of Chemistry, University of Virginia,
Charlottesville, VA 22904; GEOFFREY A. BLAKE, Division of Chemistry and Chemical Engineering and Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125; JAN M.
HOLLIS, NASA Goddard Space Flight Center, Greenbelt, MD 20771; FRANK J. LOVAS, National Institute
of Standards and Technology, Gaithersburg, MD 20899; PHILIP R. JEWELL, and ANTHONY J. REMIJAN,
National Radio Astronomy Observatory, Charlottesville, VA 22903.
FA02
THE IONIZATION TOWARD THE HIGH-MASS STAR-FORMING REGION NGC 6334 I
15 min 8:47
J. MORALES, University of Puerto Rico, Rio Piedras Campus, Physics Department, San Juan, Puerto Rico
00931; C. CECCARELI, Institut de Planétologie et d’Astrophysique de Grenoble (IPAG) UMR 5274, Grenoble, F-38041, France; L. OLMI, Osservatorio Astrofisico di Arcetri - INAF, Largo E. Fermi 5, I-50125, Firenze,
Italy; D. LIS, California Institute of Technology, Pasadena, CA 91125, USA; R. PLUME, Department of
Physics and Astronomy, University of Calgary, Calgary, AB T2N 1N4, Canada; P. SCHILKE, I. Physikalisches Institut der Universität zu Köln, Zülpicher Str. 77, 50937 Köln, Germany.
FA03
15 min 9:04
ROTATIONAL SPECTRA OF ISOTOPIC CH3 CN IN THEIR v8 = 1 EXCITED VIBRATIONAL STATES
HOLGER S. P. MÜLLER, I. Physikalisches Institut, Universität zu Köln, 50937 Köln, Germany;
B. J. DROUIN, J. C. PEARSON, Jet Propulsion Laboratory, California Institute of Technology, Pasadena,
CA 91109, USA; A. BELLOCHE, K. M. MENTEN, Max-Planck Institut für Radioastronomie, 53121 Bonn,
Germany.
FA04
15 min 9:21
THE FIRST EXTENSIVE MOLECULAR STUDY OF AN OXYGEN-RICH PLANETARY NEBULA: OBSERVATIONS
OF SiO, SO2 , AND SO
JESSICA L. EDWARDS, LUCY M. ZIURYS, Department of Chemistry and Biochemistry, Department of
Astronomy, Steward Observatory, The University of Arizona, Tucson, AZ 85721.
FA05
15 min 9:38
MAPPING THE MOLECULAR OUTFLOWS OF THE HIGH EXCITATION RED SPIDER NEBULA (NGC 6537)
96
FA06
15 min 9:55
STRUCTURE OF THE DENSE MOLECULAR GAS IN THE HELIX NEBULA: LARGE SCALE MAPPING OF HCO+
N. R. ZEIGLER, L. M. ZIURYS, Department of Chemistry, University of Arizona, PO Box 210041, 1306
East University Blvd, Tucson, AZ, 85721, USA; L. N. ZACK, Department of Chemistry, University of Basel,
Klingelbergstrasse 80, CH-4056 Basel, Switzerland.
Intermission
FA07
15 min 10:30
THE CM-, MM- AND SUBMM-WAVE SPECTRUM OF ALLYL ISOCYANIDE AND RADIOASTRONOMICAL OBSERVATIONS IN ORION KL AND THE PRIMOS LINE SURVEY
I. HAYKAL, R. A. MOTIYENKO, L. MARGULÈS, and T. R. HUET, Laboratoire PhLAM, UMR8523 CNRSUniversité Lille 1, F-59655 Villeneuve d’Ascq Cedex, France; P. ECIJA, E J. COCINERO, F BASTERRETXEA, J. A. FERNÁNDEZ, F. CASTANO, Departamento de Química Física, Facultad de Ciencia y
Tenología, Universidad del País Vasco, Barrio Sarriena s/n, 48940 Leioa (Spain); B. TERCERO, J. CERNICHARO, Centro de Astrobiología (CSIC-INTA). Ctra de Ajalvir, Km 4, 28850 Torrejón de Ardoz, Madrid,
Spain; A. LESARRI, Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47011 Valladolid (Spain); J. C. GUILLEMIN, Sciences Chimiques de Rennes -Ecole
Nationale Supérieure de Chimie de Rennes -CNRS -35700 Rennes, France.
FA08
MILLIMETER-WAVE SPECTROSCOPY OF AMINOMALONONITRILE
15 min
10:47
ROMAN A. MOTIYENKO, LAURENT MARGULÈS, Laboratoire PhLAM, UMR 8523 CNRS - Université
Lille 1, 59655 Villeneuve d’Ascq Cedex, France; JEAN-CLAUDE GUILLEMIN, Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS - ENSCR, 35708 Rennes Cedex 7, France.
FA09
15 min 11:04
TORSION-ROTATION-VIBRATION EFFECTS IN THE ν20 , 2ν21 , 2ν13 AND ν21 + ν13 STATES OF CH3 CH2 CN
ADAM M. DALY, JOHN C. PEARSON, SHANSHAN YU, BRIAN J. DROUIN, Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Dr., Pasadena, CA 91109; C. BERMÚDEZ, J. L.
ALONSO, Grupo de Espectroscopia Molecular (GEM), Edificio Quifima, Laboratorios de Espectroscopia y
Bioespectroscopia, Parque Cientfíco, Universidad de Valladolid, 47011 Valladolid, Spain.
FA10
MILLIMETER- WAVE SPECTRUM OF CARBONYL DIAZIDE IN PURSUIT OF DIAZIRINONE
15 min
11:21
BRENT K. AMBERGER, BRIAN J. ESSELMAN, R. CLAUDE WOODS and ROBERT J. McMAHON, The
University of Wisconsin - Madison Department of Chemistry, 1101 University Avenue, Madison, WI 53705.
FA11
MILLIMETER- WAVE SPECTRUM OF PYRIDAZINE
15 min
11:38
BRENT K. AMBERGER, BRIAN J. ESSELMAN, JOSH D. SHUTTER, R. CLAUDE WOODS and
ROBERT J. McMAHON, The University of Wisconsin - Madison Department of Chemistry, 1101 University Avenue, Madison, WI 53705.
FA12
Post-deadline Abstract
15 min
11:55
A LABORATORY SEARCH FOR THE CARRIER OF U-LINES ATTRIBUTED TO l-C3 H+ IN THE HORSEHEAD
NEBULA PDR
MICHAEL C. McCARTHY, KYLE N. CRABTREE, and OSCAR MARTINEZ, JR., Harvard-Smithsonian
Center for Astrophysics, Cambridge, MA 02138.
97
FB. MINI-SYMPOSIUM: THEORY AND SPECTROSCOPY
FRIDAY, JUNE 21, 2013 – 8:30 AM
Chair: STEPHEN COY, Massachusetts Institute of Technology, Cambridge, MA
FB01
INVITED TALK
ROTATIONAL SPECTROSCOPY MEETS THEORY
30 min 8:30
CRISTINA PUZZARINI, Dipartimento di Chimica "G. Ciamician", Università di Bologna, I-40126 Bologna,
Italy.
FB02
15 min 9:05
ANALYSIS OF THE MICROWAVE SPECTRUM OF THE THREE-TOP MOLECULE TRIMETHOXYLMETHANE
Créteil, France; G. FENG, AND W. CAMINATI, Dipartimento di Chimica “G. Ciamician," Università di
Bologna, Via F. Selmi, 40126 Bologna, Italy.
FB03
15 min 9:22
EXTENSION OF THE MEASUREMENT, ASSIGNMENT, AND FIT IN THE GROUND STATE OF THE TWO-TOP
MOLECULE METHYL ACETATE
H. V. L. NGUYEN, I. KLEINER, Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), UMR
7583 (CNRS/Univ. Paris Est et Paris Diderot), Université de Paris Est, 61 avenue du Général de Gaulle,
F-94010 Créteil cedex, France; S. SHIPMAN, Division of Natural Sciences, New College of Florida, 5800
Bay Shore Road, Sarasota, FL 34243-2109, USA; and K. KOBAYASHI, Department of Physics, Faculty of
Science, Toyama University, 3190 Gofuku Toyama, Toyama, 930-8555, Japan.
FB04
15 min 9:39
A FITTING PROGRAM FOR MOLECULES WITH TWO EQUIVALENT TOPS AND C2V POINT-GROUP SYMMETRY AT EQUILIBRIUM: APPLICATION TO EXISTING MICROWAVE, MILLIMETER, AND SUB-MILLIMETER
WAVE MEASUREMENTS OF ACETONE
VADIM V. ILYUSHIN, Institute of Radio Astronomy of NASU, Chervonoproporna 4, 61002 Kharkov,
Ukraine. NIST Guest Worker June - August 2009.; JON T. HOUGEN, Sensor Science Division, National
Institute of Standards and Technology, Gaithersburg, MD 20899-8441, USA.
FB05
15 min 9:56
GAS PHASE ROVIBRATIONAL SPECTROSCOPY OF DMSO, PART.I: WHEN A SYNCHROTRON SOURCE REVEALS AN UNUSUAL ROTATIONAL BEHAVIOUR
ARNAUD CUISSET, DMITRII A. SADOVSKII , Laboratoire de Physico-Chimie de l’Atmosphère, 189A
Ave. Maurice Schumann, 59140 Dunkerque, France; OLIVIER PIRALI, Ligne AILES, synchrotron SOLEIL,
L’Orme des Merisiers, Saint Aubin, BP 48, 91192 Gif-sur-Yvette, France..
FB06
15 min 10:13
GAS PHASE ROVIBRATIONAL SPECTROSCOPY OF DMSO, PART II: TOWARDS THE TERAHERTZ OBSERVATION OF 4-FOLD CLUSTERS
ARNAUD CUISSET, MARIE-ALINE MARTIN-DRUMEL, FRANCIS HINDLE, GAEL MOURET,
DMITRII A. SADOVSKII , Laboratoire de Physico-Chimie de l’Atmosphère, 189A Ave. Maurice Schumann,
59140 Dunkerque, France.
98
Intermission
FB07
WHAT IS THE NATURE OF THE DOUBLETS IN THE E-METHANOL LAMB-DIP SPECTRA?
15 min
10:45
S. P. BELOV, A.V. BURENIN, G. Yu. GOLUBIATNIKOV and A.V. LAPINOV, Institute of Applied Physics
of RAS, 46 Ul’yanova str., GSP-120, Nizhny Novgorod 603950, Russia.
FB08
15 min 11:02
ROTATIONAL SPECTROSCOPY AND QUANTUM CHEMICAL CALCULATIONS OF A FRUIT ESTER: THE MICROWAVE SPECTRUM OF n-BUTYL ACETATE
T. ATTIG, L.W. SUTIKDJA, R. KANNENGIEßER, W. STAHL, Institute of Physical Chemistry, RWTH
Aachen University, Landoltweg 2, D-52074 Aachen, Germany; I. KLEINER, Laboratoire Interuniversitaire
des Systèmes Atmosphériques, CNRS et Universités Paris Diderot et Paris Est, 61 av. Général de Gaulle,
94010, Créteil, France.
FB09
HIGH RESOLUTION THZ AND FIR SPECTROSCOPY OF SOCl2
15 min
11:19
M. A. MARTIN-DRUMEL, A. CUISSET, D. A. SADOVSKII, G. MOURET, F. HINDLE, Laboratoire de
Physico-Chimie de l’Atmosphère, EA 4493, Université du Littoral Côte d’Opale, 59140 Dunkerque, France;
O. PIRALI, Institut des Sciences Moléculaires d’Orsay, CNRS, UMR 8214, Université Paris XI, bât. 210,
91405 Orsay Cedex, France; SOLEIL Synchrotron, AILES beamline, L’orme des Merisiers, Saint-Aubin,
91192 Gif-Sur-Yvette, France.
FB10
STRUCTURE OF THE BENZENE DIMER—GOVERNED BY DYNAMICS
15 min
11:36
MELANIE SCHNELL, Center for Free-Electron Laser Science, 22761 Hamburg, Germany; Max-PlanckInstitut für Kernphysik, 69117 Heidelberg, Germany; UNDINE ERLEKAM, GERT VON HELDEN,
GERARD MEIJER, Fritz-Haber-Institut der Max-Planck-Gesellschaft, 14195 Berlin, Germany;
PHILIP R. BUNKER, National Research Council of Canada, Ottawa, Ontario K1A 0R6, Canada;
JENS-UWE GRABOW, Institut für Physikalische Chemie und Elektrochemie, Gottfried-Wilhelm-LeibnizUniverstät, 30167 Hannover, Germany; AD VAN DER AVOIRD, Institute for Molecules and Materials,
Radboud University, 6525 AJ Nijmegen, The Netherlands.
FB11
15 min 11:53
HOW TO CALCULATE SPIN-SPIN COUPLING AND SPIN-ROTATION COUPLING STRENGTHS AND THEIR UNCERTAINTIES FROM SPECTROSCOPIC DATA: APPLICATION TO THE c(13 Σ+
g ) STATE OF DIATOMIC LITHIUM
NIKESH S. DATTANI, Department of Chemistry, Oxford University, Oxford, OX1 3QZ, UK; XUAN LI,
Chemical Science Division, Lawrence Berkeley National Laboratory, Berkeley, 94720-8176, USA.
FB12
10 min 12:10
VIBRATIONAL VS ELECTRONIC POLARIZABILITY AND FIRST HYPERPOLARIZABILITY OF SOME PUSHPULL METAL PORPHYRINS
M. H. BEN ALI, Laboratoire de Chimie Théorique Computationnelle et Photonique, faculty of chemistry,
USTHB university, Algiers 16111, Algeria; A. SAAL, Department of Chemistry, UMMTO university, TiziOuzou 15000, Algeria; O. OUAMERALI, Laboratoire de Chimie Théorique Computationnelle et Photonique,
faculty of chemistry, USTHB university, Algiers 16111, Algeria.
99
FC. MICROWAVE
FRIDAY, JUNE 21, 2013 – 8:30 AM
Chair: STEPHEN COOKE, Purchase College SUNY, Purchase, NY
FC01
15 min 8:30
FLUORINE SUBSTITUTION AND COMPLEXATION EFFECTS ON FLEXIBILITY AND TUNNELING PATHWAYS: THE ROTATIONAL SPECTRUM 2-FLUOROBENZYLAMINE AND BENZYLAMINE-WATER
S. MELANDRI, A. MARIS, C. CALABRESE, L EVANGELISTI AND W. CAMINATI, Dipartimento di
Chimica Ciamician, Università di Bologna, via Selmi 2,40126 Bologna, Italy.
FC02
FTMW OBSERVATION AND ANALYSIS OF THE p-H2 –AgCl AND o-H2 –AgCl COMPLEX
15 min 8:47
G. S. GRUBBS II, DANIEL A. OBENCHAIN, HERBERT M. PICKETT and STEWART E. NOVICK, Department of Chemistry, Wesleyan University, 52 Lawn Avenue, Middletown, CT, 06459-0180, USA (email to
GSG2: [email protected]).
FC03
15 min 9:04
HYDROGEN INTERACTION WITH METAL HALIDES: THE NUCLEAR QUADRUPOLE COUPLING CONSTANT
OF GOLD IN THE p-H2 -AuCl COMPLEX AND TRENDS IN THE OTHER HYDROGEN-COINAGE METAL HALIDE
INTERACTIONS
DANIEL A. OBENCHAIN, G. S. GRUBBS II, HERBERT M. PICKETT, and STEWART E. NOVICK, Department of Chemistry, Wesleyan Univeristy, 52 Lawn Avenue, Middletown, CT, 06459-0180, USA.
FC04
THE SUBMILLIMETER SPECTRUM OF NdO
15 min 9:21
JENNIFER A. HOLT, CHRISTOPHER F. NEESE, FRANK C. DE LUCIA, Microwave Laborotory, The Ohio
State University, Columbus, Ohio 43210.
Intermission
FC05
15 min
10:00
THE ROTATIONAL SPECTRUM OF H2 S: THE H2 S ISOTOPOLOGUE AND THE SUB-DOPPLER RESOLUTION
IN THE THz REGIME
33
GABRIELE CAZZOLI, CRISTINA PUZZARINI, Dipartimento di Chimica “G. Ciamician”, Università di
Bologna, I-40126 Bologna, Italy.
FC06
15 min
10:17
EXAMINING PREBIOTIC CHEMISTRY USING O( D) INSERTION REACTIONS
1
BRIAN M. HAYS, JACOB C. LAAS, SUSANNA L. WIDICUS WEAVER, Emory University, Department of
Chemistry, Atlanta, GA 30322.
100
FC07
15 min
10:34
LABORATORY DETECTION OF IZnCH3 (X A1 ) : FURTHER EVIDENCE FOR ZINC INSERTION
1
MATTHEW P. BUCCHINO, Department of Chemistry and Biochemistry, University of Arizona, Tucson, Arizona 85721; JUSTIN P. YOUNG, Department of Chemistry, Canisius College, Buffalo, New
York 14208; PHIL M. SHERIDAN, Department of Chemistry, Canisius College, Buffalo, New York 14208;
and LUCY M. ZIURYS, Department of Chemistry and Biochemistry, Department of Astronomy, and Steward
Observatory, University of Arizona, Tucson, Arizona 85721.
FC08
15 min 10:51
FURTHER STUDIES OF POTASSIUM-BEARING MOLECULES : THE MILLIMETER-WAVE SPECTRUM OF KSH
(X1 A′ )
MATTHEW P. BUCCHINO, Department of Chemistry and Biochemistry, University of Arizona, Tucson, Arizona 85721; JUSTIN P. YOUNG, PHIL M. SHERIDAN and DAVID EWING, Department of Chemistry,
Canisius College, Buffalo, New York 14208; LUCY M. ZIURYS, Department of Chemistry and Biochemistry,
Department of Astronomy, and Steward Observatory, University of Arizona, Tucson, Arizona 85721.
FC09
ROTATIONAL SPECTRUM OF PROPARGYL ALCOHOL DIMER
15 min
11:08
DEVENDRA MANI and E. ARUNAN, Department of Inorganic and Physical Chemistry, Indian Institute of
Science Bangalore, India-560012.
101
FD. ELECTRONIC
FRIDAY, JUNE 21, 2013 – 8:30 AM
Chair: MOURAD ROUDJANE, The Ohio State University, Columbus, OH
FD01
A THEORETICAL STUDY OF CN SPECTROSCOPY FROM THE IR TO THE VUV
15 min 8:30
DAVID W. SCHWENKE, NASA Ames Research Center, Moffett Field, CA 94035.
FD02
15 min 8:47
LINE STRENGTHS IN THE FORM OF EINSTEIN A COEFFICIENTS AND OSCILLATOR STRENGTHS OF THE
A2 Π-X2 Σ+ (RED) AND B2 Σ+ -X2 Σ+ (VIOLET) SYSTEMS OF CN
R. S. RAM and J. S. A. BROOKE, Department of Chemistry, University of York, York, YO10 5DD, UK;
G. LI, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA 02138, USA; D. W. SCHWENKE,
NASA Ames Research Center, Moffett Field, CA 94035-1000, USA; P. F. BERNATH, Department of Chemistry
and Biochemistry, Old Dominion University, Norfolk, VA 23529, USA.
FD03
15 min 9:04
ARGON-INDUCED PRESSURE BROADENING, SHIFTING AND NARROWING IN THE CN Ã2 Π − X̃ 2 Σ+ (1-0)
BAND
D. FORTHOMME, C. P. MCRAVEN, T. J. SEARSa , G. E. HALL, Chemistry Department, Brookhaven National Laboratory, Bldg. 555A, P.O. Box 5000, Upton, NY 11973, USA.
a also
: Department of Chemistry, Stony Brook University, Stony Brook, New York 11794, USA
FD04
10 min 9:21
LIFETIMES OF THE Ã STATES OF C3
YI-JEN WANG, CHIAO-WEI CHEN, LIUZHU ZHOU, ANTHONY J. MERER, YEN-CHU HSU, Institute
of Atomic and Molecular Sciences, Academia Sinica, P. O. Box 23-166, Taipei 10617, Taiwan, R. O. C..
FD05
10 min 9:33
LIFETIMES OF THE Ã STATES OF THE C3 -NE AND C3 -AR COMPLEXES
YI-JEN WANG, CHIAO-WEI CHEN, ANTHONY J. MERER, YEN-CHU HSU, Institute of Atomic and
Molecular Sciences, Academia Sinica, P. O. Box 23-166, Taipei 10617, Taiwan, R. O. C..
Intermission
FD06
QUASILINEAR EVIDENCE FOR THE EQUILIBRIUM STRUCTURE OF BeOH
15 min
10:00
KYLE MASCARITOLO, JERMEY M. MERRIT, MICHAEL C. HEAVEN, Emory University, Department
of Chemistry, Atlanta, GA 30322.
102
FD07
15 min 10:17
A MODEL OF ELECTRONICALLY-EXCITED STATES OF N2 AND ITS EXTREME-ULTRAVIOLET SPECTRUM.
A.N. HEAYS, Leiden Observatory, Leiden University, P.O. Box 9513, 2300 RA Leiden, The Netherlands;
B.R. LEWIS and S.T. GIBSON, Research School of Physics and Engineering, The Australian National University, Canberra, ACT 0200, Australia.
FD08
10 min 10:34
TWO-DIMENSIONAL SUBPICOSECOND TIME-RESOLVED FLUORESCENCE ANISOTROPY: OPTICAL KERRGATING WITH A DYNAMIC POLARIZATION EXCITATION.
TAKASHIGE FUJIWARA, Department of Chemistry and Biochemistry, The Ohio State University, Columbus
OH 43210; NATALIE C. ROMANO, DAVID A. MODARELLI, and EDWARD C. LIM, Department of
Chemistry and The Center for Laser and Optical Spectroscopy, The University of Akron, Akron OH 443253601.
FD09
15 min
10:46
THE ORIGIN OF ANOMALOUS ELECTRONIC CIRCULAR DICHROISM SPECTRA OF [RuPt2 (tppz)2 Cl2 ]4+ IN
ACETONITRILE
H.-G. YUa , Department of Chemistry, Brookhaven National Laboratory, Upton, NY 11973-5000, USA.
a This work was performed at the Brookhaven National Laboratory under Contract No. DE-AC02-98CH10886 with the U.S. Department of Energy
and supported by its Division of Chemical Sciences, Office of Basic Energy Sciences, and also used the resource at NERSC.
FD10
AB INITIO STUDY OF ION-PAIR STATES OF THE IODINE MOLECULE
15 min
11:03
VADIM A. ALEKSEEV, Institute of Physics, St.Petersburg State University, Uljanovskaja St.1, Peterhof,
198504 St.Petersburg, Russia.
FD11
15 min 11:20
MEASURING THE ELECTRON ELECTRIC DIPOLE MOMENT USING YTTERBIUM FLUORIDE MOLECULES
I.J. SMALLMAN, J.A. DEVLIN, D.M. KARA, J.J. HUDSON, B.E. SAUER, M.R. TARBUTT, E.A. HINDS,
Centre for Cold Matter, Imperial College London, The Blackett Laboratory, London, SW72BW.
FD12
LASERCOOLED RaF AS A LABORATORY FOR TESTING FUNDAMENTAL SYMMETRIES
15 min
11:37
TIMUR ISAEV and ROBERT BERGER, Clemens-Schöpf Institute, Technical University of Darmstadt, 64287
Darmstadt, Germany.
FD13
PROSPECTS FOR FUNDAMENTAL SYMMETRY TESTS WITH POLYATOMIC MOLECULES
15 min
11:54
ROBERT BERGER and TIMUR ISAEV, Clemens-Schöpf Institute, Technical University of Darmstadt, 64287
Darmstadt, Germany.
FD14
15 min 12:11
ELECTRIC QUADRUPOLE TRANSITION MEASUREMENTS OF HYDROGEN MOLECULE WITH HIGH PRECISION
CUN-FENG CHENG, JIN WANG, YAN TAN, AN-WEN LIU, SHUI-MING HU, Hefei National Laboratory
for Physical Science at Microscale, University of Science and Technology of China, Hefei 230026, China.
103
FD15
15 min 12:28
QCL- AND CO2 LASER-BASED MID-IR SPECTROMETERS FOR HIGH ACCURACY MOLECULAR SPECTROSCOPY
P. L. T. SOW, B. CHANTEAU, F. AUGUSTE, S. MEJRI, S. K. TOKUNAGA, B. ARGENCE, O. LOPEZ,
C. CHARDONNET, A. AMY-KLEIN, C. DAUSSY, and B. DARQUIÉ, Laboratoire de Physique des Lasers,
Université Paris 13, Sorbonne Paris Cité, CNRS, Villetaneuse, France; D. NICOLODI, M. ABGRALL, Y.
LE COQ, LNE-SYRTE, Observatoire de Paris, CNRS, UPMC, Paris, France; G. SANTARELLI, Laboratoire
Photonique, Numérique et Nanosciences, UMR 5298 Université de Bordeaux 1, Institut d’Optique and CNRS,
Talence, France.
FD16
15 min 12:45
ACCURATE DETERMINATION OF THE BOLTZMANN CONSTANT BY DOPPLER SPECTROSCOPY TOWARDS
A NEW DEFINITION OF THE KELVIN
P. L. T. SOW, S. MERJI, S. K. TOKUNAGA, C. LEMARCHAND, M. TRIKI, C. BORDÉ, C. CHARDONNET, B. DARQUIÉ, C. DAUSSY, Laboratoire de Physique des Lasers, Université Paris 13, Sorbonne Paris
Cité, CNRS, F-93430, Villetaneuse, France.
104
FE. DYNAMICS
FRIDAY, JUNE 21, 2013 – 8:30 AM
Chair: TERRY GUSTAFSON, The Ohio State University, Columbus, OH
FE01
15 min 8:30
CRYOGENIC ION VIBRATIONAL SPECTROSCOPY OF PT(II)-METHANE CH ACTIVATION INTERMEDIATES
BRETT MARSH, ETIENNE GARAND, Department of Chemistry, University of Wisconsin-Madison, Madison, WI 53706.
FE02
EXPERIMENTAL CHARACTERIZATION OF IDEALIZED METAL-CENTERED REACTIONS
15 min 8:47
DARRIN BELLERT, ADAM MANSELL, and ZACHARY THEIS, Department of Chemistry, Baylor University, Waco, TX 76798.
FE03
15 min 9:04
UTILIZING METAL TO LIGAND CHARGE TRANSFER STATES OF MM QUADRUPLY BONDED COMPLEXES
FOR PHOTOVOLTAIC APPLICATIONS
SHARLENE A. LEWIS, SAMANTHA E. BROWN-XU, MALCOLM H. CHISHOLM, The Ohio State University, Department of Chemistry and Biochemistry, Columbus, Ohio 43210; ARTHUR J. EPSTEIN, The
Ohio State University, Department of Chemistry and Biochemistry and Department of Physics, Columbus,
Ohio 43210.
FE04
15 min 9:21
VIBRATIONALLY DRIVEN HYDROGEN ABSTRACTION REACTION BY BROMINE RADICAL IN SOLUTION
JAE YOON SHIN, MICHAEL A. SHALOWSKI, and F. FLEMING CRIM, Department of Chemistry, University of Wisconsin-Madison, WI 53706.
FE05
15 min 9:38
STRUCTURAL MOTIONS AND CHARGE DELOCALIZATION IN ELECTRONICALLY EXCITED N, N ′ DIMETHYLPIPERAZINE
XINXIN CHENG , Department of Chemistry, Brown University, Providence, RI 02912; SANGHAMITRA DEB , Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104; and PETER M. WEBER , Department of Chemistry, Brown University, Providence, RI 02912.
Intermission
FE06
15 min
THEORETICAL STUDIES OF PHOTODISSOCIATION DYNAMICS OF BRCN
10:10
−
BERNICE OPOKU-AGYEMAN and ANNE B. McCOY, Department of Chemistry and Biochemistry, The
Ohio State University, Columbus, OH 43210.
105
FE07
USING TRYPTOPHAN AS A PROBE FOR STUDYING PROTEIN HYDRATION DYNAMICS
15 min
10:27
YANGZHONG QIN, CHIH-WEI CHANG, LIJUAN WANG AND DONGPING ZHONG, DEPARTMENT
OF PHYSICS, THE OHIO STATE UNIVERSITY, COLUMBUS, OH, 43210.
FE08
15 min 10:44
FEMTOSECOND CONICAL INTERSECTION DYNAMICS OF TRYPTOPHAN IN PROTEINS AND VALIDATION
OF SLOWDOWN OF HYDRATION LAYER DYNAMICS
J. YANG, Department of Physics, The Ohio State University, Columbus, OH 43210; L. ZHANG, Department of Chemistry, Columbia University, New York, NY 10027; L. WANG, and D. ZHONG, Department of
Physics, Department of Chemistry and Biochemistry, and Programs of Biophysics, Chemical Physics, and
Biochemistry, The Ohio State University, Columbus, OH 43210.
FE09
PHOTOISOMERIZATION DYANAMICS OF THE SUNSCREEN MOLECULE AVOBENZONE
15 min
11:01
ADAM D. DUNKELBERGER, RYAN D. KIEDA, and F. FLEMING CRIM, Department of Chemistry, University of Wisconsin-Madison, Madison, WI 53706.
FE10
STUDY OF PROTON TRANSFER IN E. COLI PHOTOLYASE
15 min
11:18
MENG ZHANG, ZHEYUN LIU, JIANG LI, LIJUAN WANG and DONGPING ZHONG, 191 W. Woodruff
Ave., Columbus, Ohio 43210..
FE11
15 min 11:35
DETECTION AND INTERPRETATION OF COLLISIONAL TRANSFER AND ROTATIONAL ANISOTROPY FINGERPRINTS IN RESONANT FOUR-WAVE MIXING SPECTRA.
A. KOUZOV, Department of Physics, Saint-Petersburg State University, Peterhof, Saint-Petersburg 198504,
Russia; P. RADI, P. MAKSYUTENKO, Department General Energy, Paul Scherrer Institute, CH-5232 Villigen, Switzerland; and D. KOZLOV, A.M. Prokhorov General Physics Institute, Russian Academy of Sciences,
Vavilov str. 38, 119991 Moscow, Russia.
FE12
15 min 11:52
USING TERAHERTZ SPECTROSCOPY TO STUDY SYSTEMS WITH SOLAR ENERGY APPLICATIONS
REBECCA L. MILOT, GARY F. MOORE, LAUREN A. MARTINI, GARY W. BRUDVIG, ROBERT H.
CRABTREE, and CHARLES A. SCHMUTTENMAER, Department of Chemistry, Yale University, New
Haven, CT 06520-8107.
106
MA. PLENARY
MONDAY, JUNE 17, 2013 – 8:45 AM
Chair: FRANK C. DE LUCIA, The Ohio State University, Columbus, OH
Welcome
Caroline C. Whitacre, Vice President for Research
The Ohio State University
MA01
LOW TEMPERATURE TRAPPING: FROM REACTIONS TO SPECTROSCOPY
8:45
40 min 9:00
S. SCHLEMMER, O. ASVANY, and S. BRÜNKEN, I. Physikalisches Institut, Universität zu Köln,
50937 Köln, Germany.
The kinetics of ion - molecule reactions are investigated in higher-order multipole traps by observation of the temporal
evolution of mass selected parent ions in the presence of a neutral reaction partner. Rate coeffients for fast reactions
(proceeding at collision rate) and very slow reactions (taking millions of collisions) are determined over a wide range of
temperatures. Endothermic or hindered reactions can be promoted by excitation of the ion via absorption of a photon.
Scanning the photon energy while detecting the number of product ions establishes an action spectroscopy method which
we developed over the last 10-15 years and termed LIR: laser or light induced reactions. a The main advantages of LIR
are mass selection of the parent ion and low temperature conditions in the trap. Long storage times in combination with a
near unity detection efficiency make LIR one of the most sensitive spectroscopy methods. The status quo of LIR will be
c
discussed on selected examples. Recent measurements are concerned with ro-vibrational spectra of CH2 D+ b and CH+
5
+
at highest resolution using cw OPO radiation. In the particular case of CH5 , the lines in the mid IR have been measured
at a nominal temperature of 10 K and a frequency comb has been used for absolute calibration. Line positions can be
determined to an accuracy which shall enable us in the future to obtain rotational spectra in a THz-IR double resonance
approach. We tested the feasibility of this two photon method recently on H2 D+ .
a S. Schlemmer, T. Kuhn, E. Lescop, and D. Gerlich, Laser excited N+ in a 22-Pole Trap: Experimental Studies of Rotational Relaxation Processes,
2
Int. J. Mass Spectrometry and Ion Processes, 185-187, 589-602, (1999), S.D. Ivanov, O. Asvany, A. Witt, E. Hugo, G. Mathias, B. Redlich, D. Marx and
S. Schlemmer, Quantum-induced symmetry breaking explains infrared spectra of CH+
5 isotopologues, Nature Chemistry, 2, 298302 (2010)
b S. Gaertner, J. Krieg, A. Klemann, O. Asvany and S. Schlemmer, Rotational transitions of CH D+ determined by high-resolution IR spectroscopy,
2
Astron. Astrophys., 516 (2010) L3.
c O. Asvany, J. Krieg, and S. Schlemmer, Frequency comb assisted mid-infrared spectroscopy of cold molecular ions, Rev.Sci.Instr., 83 (2012), 076102.
MA02
DECODING THE EFFECTS OF LARGE AMPLITUDE VIBRATIONAL MOTIONS IN SPECTRA
40 min 9:45
ANNE B. McCOY, LAURA C. DZUGAN, MENG HUANG, ZHOU LIN, BERNICE OPOKU-AGYEMAN,
ANDREW S. PETIT, JASON FORD, and BETHANY A. WELLEN, Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH 43210.
Over the past decades significant progress has been made, which allows spectroscopists to interpret vibrational spectra of
molecules that undergo small amplitude displacements from their equilibrium structure. Based on these assignments, one
can obtain insights into the structure and bonding of the molecule that is being studied through the use of model Hamiltonians. In this talk, we focus on systems that undergo large amplitude vibrational motions, and where the anharmonicities
are manifested in unexpected intensity patterns in the vibrational spectrum. Theoretical and computational approaches
used to address such questions will be described, with an emphasis on our group’s work on diffusion Monte Carlo approaches. The ideas will be illustrated through discussions of a variety of protonated and hydrogen bonded systems of
current experimental interest including H+
5 , molecules and ions that have intermolecular hydrogen bonds, and ion-water
complexes.
Intermission
107
RAO AWARDS
Presentation of Awards by Yunjie Xu, University of Alberta
10:50
2012 Rao Award Winners
Nils Bartels, Georg August Universitaet Goettingen
Andrew Petit, The Ohio State University
Arron Wolk, Yale University
COBLENTZ AWARD
Presentation of Award by Michael L. Myrick, President, Coblentz Society
5 min
11:05
MA03
40 min
11:10
Coblentz Society Award Lecture
LINEAR AND NONLINEAR MOLECULAR SPECTROSCOPY WITH LASER FREQUENCY COMBS
NATHALIE PICQUÉ, Max Planck Institut für Quantenoptik, Hans-Kopfermann-Str. 1, 85748 Garching, Germany; Ludwig-Maximilians-Universität München, Fakultät für Physik, Schellingstrasse 4/III, 80799 München,
Germany; Institut des Sciences Moléculaires d’Orsay, Université Paris-Sud, 91405 Orsay, France; email:
[email protected].
The regular pulse train of a mode-locked femtosecond laser can give rise to a comb spectrum of millions of laser modes
with a spacing precisely equal to the pulse repetition frequency. Laser frequency combs were conceived a decade ago as
tools for the precision spectroscopy of atomic hydrogen. They are now becoming enabling tools for an increasing number
of applications, including molecular spectroscopy.
Recent experiments of multi-heterodyne frequency comb Fourier transform spectroscopy (also called dual-comb spectroscopy) have demonstrateda that the precisely spaced spectral lines of a laser frequency comb can be harnessed for new
techniques of linear absorption spectroscopy. The first proof-of-principle experiments have demonstrated a very exciting potential of dual-comb spectroscopy without moving parts for ultra-rapid and ultra-sensitive recording of complex
broad spectral bandwidth molecular spectra. Compared to conventional Michelson-based Fourier transform spectroscopy,
recording times could be shortened from seconds to microseconds, with intriguing prospects for spectroscopy of short lived
transient species. The resolution improves proportionally to the measurement time. Therefore longer recordings allow high
resolution spectroscopy of molecules with extreme precision, since the absolute frequency of each laser comb line can be
known with the accuracy of an atomic clock.
Moreover, since laser frequency combs involve intense ultrashort laser pulses, nonlinear interactions can be harnessed.
Broad spectral bandwidth ultra-rapid nonlinear molecular spectroscopy and imaging with two laser frequency combs is
demonstratedb with coherent Raman effects and two-photon excitation. Real-time multiplex accessing of hyperspectral
images may dramatically expand the range of applications of nonlinear microscopy.
a B. Bernhardt et al., Nature Photonics 4, 55-57 (2010); A. Schliesser et al. Nature Photonics 6, 440-449 (2012); T. Ideguchi et al. arXiv:1201.4177
(2012)
b T. Ideguchi et al., Optics letters 37, 4498-4500 (2012); T. Ideguchi et al. arXiv:1302.2414 (2013)
108
MF. MINI-SYMPOSIUM: SPECTROSCOPY TESTS OF FUNDAMENTAL
PHYSICS
MONDAY, JUNE 17, 2013 – 1:30 PM
Chair: TIMOTHY STEIMLE, Arizona State University, Tempe, AZ
MF01
INVITED TALK
SEARCH FOR A VARIATION OF FUNDAMENTAL CONSTANTS
30 min 1:30
W. UBACHS, Department of Physics and Astronomy, VU University Amsterdam, De Boelelaan 1081, 1081
HV Amsterdam, Netherlands.
Since the days of Dirac scientists have speculated about the possibility that the laws of nature, and the fundamental constants appearing in those laws, are not rock-solid and eternal but may be subject to change in time or space. Such a scenario
of evolving constants might provide an answer to the deepest puzzle of contemporary science, namely why the conditions
in our local Universe allow for extreme complexity: the fine-tuning problem. In the past decade it has been established
that spectral lines of atoms and molecules, which can currently be measured at ever-higher accuracies, form an ideal test
ground for probing drifting constants. This has brought this subject from the realm of metaphysics to that of experimental
science. In particular the spectra of molecules are sensitive for probing a variation of the proton-electron mass ratio µ,
either on a cosmological time scale, or on a laboratory time scale. A comparison can be made between spectra of molecular hydrogen observed in the laboratory and at a high redshift (z=2-3), using the Very Large Telescope (Paranal, Chile) a
and the Keck telescope (Hawaii) b . This puts a constraint on a varying mass ratio ∆µ/µ at the 10−5 level. The optical
work can also be extended to include CO molecules c . Further a novel direction will be discussed: it was discovered that
molecules exhibiting hindered internal rotation have spectral lines in the radio-spectrum that are extremely sensitive to a
varying proton-electron mass ratio. Such lines in the spectrum of methanol were recently observed with the radio-telescope
in Effelsberg (Germany) d .
a F.
van Weerdenburg, M.T. Murphy, A.L. Malec, L. Kaper, W. Ubachs, Phys. Rev. Lett. 106, 180802 (2011).
Malec, R. Buning, M.T. Murphy, N. Milutinovic, S.L. Ellison, J.X. Prochaska, L. Kaper, J. Tumlinson, R.F. Carswell, W. Ubachs,
Mon. Not. Roy. Astron. Soc. 403, 1541 (2010).
c E.J. Salumbides, M.L. Niu, J. Bagdonaite, N. de Oliveira, D. Joyeux, L. Nahon, W. Ubachs, Phys. Rev. A 86, 022510 (2012).
d J. Bagdonaite, P. Jansen, C. Henkel, H.L. Bethlem, K. Menten, W. Ubachs, Science 339, 46 (2013).
b A.
109
MF02
AN ALCOHOL TEST FOR DRIFTING CONSTANTS
15 min 2:05
P. JANSEN, J. BAGDONAITE, W. UBACHS and H.L. BETHLEM, Institute for Lasers, Life and Biophotonics, VU University Amsterdam, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands; I. KLEINER,
Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), CNRS UMR 7583 et Universités Paris
Diderot et Paris Est, 61 av. Général de Gaulle, 94010 Créteil Cédex, France; L.-H. XU, Department of
Physics and Centre for Laser, Atomic, and Molecular Sciences, University of New Brunswick, Saint John, New
Brunswick E2L 4L5, Canada.
143.924
E1
Energy(cm-1)
¾
139.416 AThe Standard Model of physics is built on the fundamenE2
400
139.388 A+
A∓ νt=1
tal constants of nature, however without providing an ex133.173 E2
E1
300
planation for their values, nor requiring their constancy
over space and time. Molecular spectroscopy can address
a
200
νt=0
V
this issue. Recentlya , we found that microwave transitions
c
b
in methanol are extremely sensitive to a variation of the
100
proton-to-electron mass ratio µ, due to a fortuitous inter0
play between classically forbidden internal rotation and ro0
π/3 2π/3
π
4π/3 5π/3 2π
tation of the molecule as a whole. In this talk, we will
Torsionalangleγ(rad)
explain the origin of this effect and how the sensitivity coefficients in methanol are calculated. In addition, we set a
limit on a possible cosmological variation of µ by comparing transitions in methanol observed in the early Universe with
those measured in the laboratory. Based on radio-astronomical observations of PKS1830-211, we deduce a constraint of
∆µ/µ = (0.0 ± 1.0) × 10−7 at redshift z = 0.89, corresponding to a look-back time of 7 billion yearsb . While this limit
is more constraining and systematically more robust than previous ones, the methanol method opens a new search territory
for probing µ-variation on cosmological timescales.
a P.
b J.
Jansen, L.-H. Xu, I. Kleiner, W. Ubachs, and H.L. Bethlem Phys. Rev. Lett. 106(100801) 2011.
Bagdonaite, P. Jansen, C. Henkel, H.L. Bethlem, K.M. Menten, and W. Ubachs Science 339(46) 2013.
MF03
15 min 2:22
SENSITIVITY OF TRANSITIONS IN INTERNAL ROTOR MOLECULES TO A POSSIBLE VARIATION OF THE
PROTON-TO-ELECTRON MASS RATIO
P. JANSEN, W. UBACHS, H. L. BETHLEM, Institute for Lasers, Life and Biophotonics, VU University
Amsterdam, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands; I. KLEINER, Laboratoire Interuniversitaire des Systèmes Atmosphériques, CNRS et Universités Paris Diderot et Paris Est, 61 av. Général de
Gaulle, 94010, Créteil, France; L-H. XU, Department of Physics and Centre for Laser, Atomic and Molecular
Sciences, University of New Brunswick, Saint John, New Brunswick E2L 4L5, Canada.
Recently, methanol was identified as a sensitive target system to probe variations of the proton-to-electron mass ratio.a
The high sensitivity of methanol originates from the interplay between overall rotation and hindered internal rotation of
the molecule and it gives rise to a large enhancement of the sensitivity coefficient,Kµ. In this talk we will remind the
general concepts that form the foundation of the high sensitivity in methanol and the approximate model which allows to
estimate the sensitivities of transitions in internal rotor molecules with C3v symmetry, without performing a full calculation
of energy levels. We will show some examples by comparing obtained sensitivities for methanol, acetaldehyde, acetamide,
methyl formate and acetic acid with a full analysis using the molecular Hamiltonian. The talk will give some details about
how we obtain the energy levels from the BELGI code. From the molecules considered, methanol appears to be the most
suitable candidate for laboratory and cosmological tests searching for a possible variation of µ.
a Jansen
et al. Phys. Rev. Lett 106, 100801 (2011)
110
MF04
CH3 OH SUB-DOPPLER SPECTROSCOPY
15 min 2:39
GERMAN YU. GOLUBIATNIKOV, SERGEY P. BELOV and ALEXANDER V. LAPINOV, Institute of Applied Physics of RAS, 46 Ulyanov str., 603950 Nizhny Novgorod, Russia.
The methanol torsion-rotation spectrum in the first three torsional states has been measured and analysed for a search of
me /mp variations from comparison of radio astronomical and laboratory frequencies and for studies of systematic velocity
motions in star-forming regions. The investigation is based on Lamb-dip measurements with sub-Doppler spectrometer
developed at IAP RAS. CH3 OH-A and -E frequencies have been obtained with an accuracy of ∼1 kHz at 48−510 GHz for
more than 500 transitions in vt = 0, more than 200 transitions in vt = 1 and 100 transitions in vt = 2. For many b-type
transitions the removed degeneracy of the CH3 OH levels due to different nuclear spin statistics was measured in a form of
doublets with unresolved hf structure. Some a-type transitions show resolved spin-rotational splitting.
MF05
15 min 2:56
HIGH RESOLUTION MICROWAVE SPECTROSCOPY OF CH AS A SEARCH FOR VARIATION OF FUNDAMENTAL CONSTANTS
S. TRUPPE, R. J. HENDRICKS, S. K. TOKUNAGA, E. A. HINDS, M. R. TARBUTT, Centre for Cold Matter,
Blackett Laboratory, Imperial College London, London, SW7 2BW.
The Standard Model of particle physics assumes that fundamental, dimensionless constants like the fine-structure constant,
α, or the ratio of the proton to electron mass, µ, remain constant through time and space. Laboratory experiments have
set tight bounds on variations of such constants on a short time scalea . Astronomical observations, however, provide vital
information about possible changes on long time scales. Recent measurements using quasar absorption spectra provide
some evidence for a space-time variation of the fine-structure constant αb . It is thus important to verify this discovery by
using an entirely different method. Recently the prospect of using rotational microwave spectra of molecules as a probe
of fundamental constants variation has attracted much attentionc. Generally these spectra depend on µ, but if fine and
hyperfine structure is involved they also become sensitive to variations of α and the nuclear g-factor. Recent calculationsd,e
show that the Λ-doublet and rotational spectra of CH are particularly sensitive to possible variations of µ and α. We
present recent laboratory based high-resolution spectra of the Λ-doublet transition frequencies of the F2 , J = 1/2 and F1 ,
J = 3/2 states of CH, X 2 Π (v=0) at 3.3GHz and 0.7GHz respectively, with F labelling the different spin-orbit manifolds
of CH. We also present a measurement of the transition frequency between the two spin-orbit manifolds F2 , J=1/2 and F1 ,
J=3/2 at 530GHz. By using a molecular beam of CH in combination with a laser-microwave double-resonance technique
and Ramsey’s method of separated oscillatory fields, we have measured these transition frequencies to unprecedented
accuracy. Hence CH can now be used as a sensitive probe to detect changes in fundamental constants by comparing lab
based frequencies to radio-astronomical observations from distant gas clouds.
a T.
Rosenband et al., Science 319(5871), 1808, 2008
K. Webb et al., Physical Review Letters 107(19), 191101, 2011
c V. V. Flambaum et al., Physical Review A 99(15), 150801, 2007
d M. G. Kozlov, Physical Review A 80(2), 022118, 2009
e A. J. de Nijs et al., Physical Review A 86(3), 032501, 2012
b J.
111
MF06
SUB-DOPPLER AND FTMW SPECTROSCOPY OF HC3 N ISOTOPOLOGUES
15 min 3:13
A.V. LAPINOV, G. YU. GOLUBIATNIKOV, Institute of Applied Physics of RAS, 46 Ulyanov str., 603950
Nizhny Novgorod, Russia; A. P. VELMUZHOV, Institute of Metalloorganic Chemistry of RAS, 49 Tropinin
str., 603950 Nizhny Novgorod, Russia; J.-U. GRABOW, Institute of Physical Chemistry and Electrochemistry,
Leibniz University of Hannover, Callinstrasse 3A, 30167 Hannover, Germany; and A. GUARNIERI, Technical
Faculty of Christian Albrecht University of Kiel, Kaiserstrasse 2, 24143 Kiel, Germany.
We report results of precise sub-Doppler spectroscopy of HC3 N, H13 CCCN, HC13 CCN, HCC13 CN and HCCC15 N at
45−510 GHz with Lamb-dip spectrometer of IAP RAS. Hf structure of rotational transitions of all above species below
27 GHz as well as inversion transitions of NH3 (1,1) and (2,2) were measured using FTMW spectrometer of University
of Hannover. New comparison of HC3 N and NH3 laboratory frequencies with radio astronomical observations of dark
cloudsa,b shows an upper limit of me /mp variation in our Galaxy as ≤ 3 · 10−9 .
a S.
b S.
A. Levshakov, A. V. Lapinov, C. Henkel et al. Astron. Astrophys. 524, A32, 2010.
A. Levshakov, P. Molaro, A. V. Lapinov et al. Astron. Astrophys. 512, A44, 2010.
MF07
15 min 3:30
THE CO A-X SYSTEM FOR CONSTRAINING COSMOLOGICAL DRIFT OF THE PROTON-ELECTRON MASS
RATIO
M. L. NIU, E. J. SALUMBIDES, D. ZHAO, J. BAGDONAITE, Department of Physics and Astronomy, and
LaserLaB, VU University, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands; N. DE OLIVEIRA,
D. JOYEUX, L. NAHON, Synchrotron Soleil, Orme des Merisiers, St Aubin BP 48, 91192, GIF sur Yvette
cedex, France; R. W. FIELD, Department of Chemistry, Massachusetts Institute of Technology, Cambridge,
Massachusetts 02139, USA; and W. UBACHS, Department of Physics and Astronomy, and LaserLaB, VU
University, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands.
The A1 Π − X1 Σ+ band system of carbon monoxide, which has been detected in six highly redshifted galaxies (z =
1.6 − 2.7), is identified as a novel probe method to search for possible variations of the proton-electron mass ratio (µ) on
cosmological time scales. Laboratory wavelengths of the spectral lines of the A-X (v,0) bands for v = 0 − 9 have been
determined at an accuracy of ∆λ/λ = 1.5 × 10−7 through VUV Fourier-transform absorption spectroscopy, providing a
comprehensive and accurate zero-redshift data seta . Two-photon Doppler-free laser spectroscopy has been applied for the
(0,0) and (1,0) bands, achieving 3×10−8 accuracy level, verifying the absorption data. Accurate sensitivity coefficients Kµ
for a varying µ have been calculated for the CO A-X bands, so that an operational method results to search for µ-variation.
The data from both experiments were used to perform an improved analysis of the perturbations in the A1 Π, v = 0 and 1
levels by vibrational levels in the D1 ∆, I1 Σ− , e3 Σ− , d3 ∆, and a′3 Σ+ states. The object Q1237+064 will be observed in
May 2013, aiming for a good signal-to-noise spectrum containing the CO A-X bands as well as the H2 Lyman and Werner
bands. This should result in an accurate and robust constraint on ∆µ/µ.
a E.J.
Salumbides, M.L. Niu, J. Bagdonaite, N. de Oliveira, D. Joyeux, L. Nahon and W. Ubachs, Phys. Rev. A 86, 022510 (2012).
112
MF08
PRECISE MEASUREMENT OF
15 min 3:47
40
CaH VIBRATIONAL TRANSITION FREQUENCY
+
MASATOSHI KAJITA, Nat. Ins. Info. Comm. Tech., Koganei, Tokyo 184-8795, Japan; MINORI ABE, Dep.
of Chemistry, Tokyo Metro. Univ., Hachioji, Tokyo 192-0397, Japan.
Small number of molecular ions in a linear trap can be sympathetically cooled with atomic ions and form a string crystal at
the position, where the electric field is zero. Molecular ions in a strinc crystal are advantageous to measure the transition
frequencies without Stark shift induced by the trap electric field, but it is required to localize small number of molecular
ions in a single quantum state. 40 CaH+ molecular ion is advantageous to solve this problem, because (1) molecular ion with
rotational constant of 141 GHz is localized in the vibrational-rotational ground state when the surrounding temperature is
lower than 10 K, and (2) there is no hyperfine splitting in the J = 0 state.
In this presentation, we porpose to measure the 40 CaH+ X 1 Σ (v, N, F, M ) = (0, 0, 1/2, ±1/2) →
(vu , 0, 1/2, ±1/2) (vu = 1, 2, 3, , , ) transition with the uncertainty lower than 10−16 . With these transitions, Zeeman shift
is less than 10−16 /G (given by the slight dependence of schielding effect by electron cloud on the vibrational state) and
electric quadrupole shift is zero because of F = 1/2.
The J = 0 → 0 transition is one-photon forbidden, and it can be observed also by Raman transition using two lasers. Stark
shift induced by Raman lasers actually dominates the measurement uncertainty. When v = 0 → 1 transition is observed
using Raman lasers in the 6000-15000 /cm, Stark shift with saturation power is of the order of 1.5 × 10−14 and it is higher
for overtone transitions. With the following Raman laser frequencies, total Stark shift induced by two Raman lasers is zero.
v = 0 → 1 24527 /cm and 23079 /cm v = 0 → 2 24600 /cm and 21745 /cm
v = 0 → 3 26237 /cm and 22017 /cm v = 0 → 4 25354 /cm and 19814 /cm
The 40 CaH+ X 1 Σ (v, N, F, M ) = (0, 0, 1/2, ±1/2) → (vu , 0, 1/2, ±1/2) (vu = 1, 2, 3, , , ) transition can be measured
with the uncertainty lower than 10−16 , and it is useful to test the variation in the proton-to-electron mass ratio.
MF09
15 min 4:04
PRECISE MEASUREMENT OF VIBRATIONAL TRANSITION FREQUENCY OF OPTICALLY TRAPPED
MOLECULES
MASATOSHI KAJITA, Nat. Ins. Info. Comm. Tech., Koganei, Tokyo 184-8795, Japan; GEETHA GOPAKUMAR,MINORI ABE, and MASAHIKO HADA, Dep. of Chemistry, Tokyo Metro. Univ., Hachioji, Tokyo
192-0397, Japan.
We propose to measure the X 2 Σ (v, N, F, M ) = (0, 0, 3/2, ±3/2) → (vu , 0, 3/2, ±3/2) (vu = 1, 2, 3, 4, , , , ) transition
frequencies of X6 Li molecules with the uncertainty lower than 10−16 (X: 174 Yb, 88 Sr, 40 Ca). Molecules are produced
by photo-association of cold atoms and trapped in the optical lattices. Measurement with molecules in optical lattices is
particularly advantageous for precision measurements because (1) the molecules and probe laser interact for a long time, (2)
molecules are localized within the Lamb-Dicke region, (3) the measurement is possible with a large number of molecules,
and (4) collision effects are suppressed (molecules are trapped at different positions in 2D lattices).
Using the proper trap laser frequency, the Stark shift induced by the trap laser is eliminated as the Stark energy shift of the
upper and lower states are equal (magic frequency). When the trap laser frequency is shifted from the magic frequency by
1 MHz, the Stark shift is less than 3 × 10−15 .
The N = 0 → 0 transition is one-photon forbidden, and it is stimulated by Raman transition using two lasers. When one
of two Raman lasers is higher than the magic frequency and another is lower, the total Stark shift induced by two Raman
lasers can be eliminated.
Measurement of molecular vibrational transition frequencies is useful to test the variation in the proton-to-electron mass
ratio. The 1 S0 -3 P0 transition frequencies of 27 Al+ ion or 87 Sr atom are useful as the reference.
Intermission
113
MF10
15 min 4:36
TOWARDS MORE ACCURATE MEASUREMENTS OF THE IONIZATION ENERGY OF MOLECULAR HYDROGEN
D. SPRECHER, M. BEYER, J. LIU, and F. MERKT, ETH Zürich, Laboratorium für Physikalische Chemie,
Wolfgang-Pauli-Strasse 10, 8093 Zürich, Switzerland; E. SALUMBIDES, K. S. E. EIKEMA, W. UBACHS,
Department of Physics and Astronomy, Laser Centre, Vrije Universiteit, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands; CH. JUNGEN, Laboratoire Aimé Cotton, CNRS II, Bâtiment 505, Campus d’Orsay,
91405 Orsay Cedex, France.
With two electrons and two protons, molecular hydrogen is the simplest molecule displaying all features of a chemical
bond. H2 is therefore a fundamental system for testing molecular quantum mechanics and quantum electrodynamics in
molecules. The test can be performed by comparing measured and calculated intervals between different rovibronic states
of H2 a .
Two further quantities that can be used for this test are the dissociation and ionization energies of H2 , and considerable
efforts have been invested over more than 80 years to improve the precision and accuracy of experimental and theoretical
determination of these two quantities. The current status of the comparison is that the theoretical b and experimental c
values of the ionization and dissociation energies of H2 agree within the combined uncertainty of 30 MHz (see also d ).
The factors currently limiting the precision of the experimental determination will be discussed and the strategies that are
being implemented towards overcoming these limitations will be presented. A long-term goal is to achieve a precision of
better than 15 kHz, which is the ultimate limit imposed on the accuracy of the theoretical determination by the current
uncertainty of the proton-to-electron mass ratio.
a E. J.
Salumbides, G. D. Dickenson, T. I. Ivanov and W. Ubachs, Phys. Rev. Lett. 107 (4), 043005 (2011).
Piszczatowski, G. Łach, M. Przybytek, J. Komasa, K. Pachuckiand and B. Jeziorski, J. Chem. Theory Comput. 5 (11), 3039 (2009).
c J. Liu, E. J. Salumbides, U. Hollenstein, J. C. J. Koelemeij, K. S. E. Eikema, W. Ubachs and F. Merkt, J. Chem. Phys. 130 (17), 174306 (2009).
d D. Sprecher, Ch. Jungen, W. Ubachs and F. Merkt, Faraday Discuss. 150, 51 (2011).
b K.
MF11
NON-ADIABATIC ENERGIES OF THE HYDROGEN MOLECULE
15 min 4:53
A novel perturbation theory has been developed to account for nonadiabatic effects in diatomic moleculesa. All molecular
levels can be obtained simultanously from a single nuclear equation corrected for the presence of (m/M )2 terms. Comparison with the direct nonadiabatic calculations for rotationless states of H2 demonstrates an agreement at the level of 10−5
cm−1 for the ground tone transition.
a K.
Pachucki and J. Komasa, J. Chem. Phys. 130, 164113 (2009)
MF12
QED EFFECTS IN H2
15 min 5:10
The electron self-interaction and the vacuum polarization, the two effects predicted by Quantum Electrodynamics (QED),
have been accurately calculated for H2 and its isotopomersa. The resulting theoretical predictions will be compared with
state of the art measurements of dissociation energies, vibrational and rotational transitions. New developments for the
calculation of higher order QED effects will be presented.
a J.
Komasa, K. Piszczatowski, G. Łach, M. Przybytek, B. Jeziorski, and K. Pachucki, JCTC 7, 3105 (2011)
114
MF13
PRECISION MEASUREMENT OF THE IONIZATION ENERGY OF THE GK
MOLECULAR HYDROGEN.
15 min 5:27
1
Σ+
g
(v = 1, N = 1) STATE OF
M. BEYER, D. SPRECHER and F. MERKT, ETH Zürich, Laboratorium für Physikalische Chemie, WolfgangPauli-Strasse 10, 8093 Zürich, Switzerland.
The ionization energy of the GK 1 Σ+
g (v = 1, N = 1) state of ortho H2 has been determined at a precision of 1.2 MHz by
near-infrared laser spectroscopy.
The measurement was performed by first exciting molecular hydrogen from the X 1 Σ+
g (v = 0, N = 1) state to the
1 +
GK 1 Σ+
g (v = 1, N = 1) state in a resonant two-photon process via the B Σu (v = 3, N = 2) state and then measuring
the frequency of the transition between the GK 1 Σ+
g (v = 1, N = 1) state and the 56p (S = 0, N = 1) Rydberg state
+
belonging to the series converging on the X + 2 Σ+
(v
= 0, N + = 1) ground state of ortho H+
g
2 . The ionization energy of
1 +
the GK Σg (v = 1, N = 1) state was obtained by adding this frequency to the binding energy of the 56p (S = 0, N = 1)
Rydberg state which has been determined previously by millimeter-wave spectroscopy and multichannel quantum-defect
theory a b .
For the measurement we used a homebuilt pulsed NIR laser with Fourier-transform-limited linewidth and adjustable pulse
duration. To reach the desired accuracy, systematic errors originating from ac and dc Stark shifts, from pressure shifts, and
from the frequency shifts and chirps accompanying the generation of the NIR laser pulses were quantified. The ionization
c d
.
energy of the GK 1 Σ+
g (v = 1, N = 1) state will be compared with earlier results
1 +
New attempts of measuring the binding energy of the EF Σg state will also be mentioned.
a A.
Osterwalder, A. Wüest, F. Merkt and Ch. Jungen, J. Chem. Phys. 121 (23), 11810 (2004).
Sprecher, Ch. Jungen, W. Ubachs and F. Merkt, Faraday Discuss. 150, 51 (2011).
c Ch. Jungen, I. Dabrowski, G. Herzberg and M. Vervloet, J. Chem. Phys. 93 (4), 2289 (1990).
d D. Bailly, E. J. Salumbides, M. Vervloet and W. Ubachs, Mol. Phys. 108 (7-9), 827 (2010).
b D.
MF14
QED TESTS AND SEARCH FOR NEW PHYSICS IN MOLECULAR HYDROGEN
15 min 5:44
E. J. SALUMBIDES, M. L. NIU, G. D. DICKENSON, K. S. E. EIKEMA, Department of Physics and Astronomy, and LaserLaB, VU University, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands; J. KOMASA,
Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland; K. PACHUCKI, Faculty of Physics, University of Warsaw, Hoża 69, 00-681 Warsaw, Poland; and W. UBACHS, Department of
Physics and Astronomy, and LaserLaB, VU University, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands.
The hydrogen molecule has been the benchmark system for quantum chemistry, and may provide a test ground for new
a
physics. We present our high-resolution spectroscopic studies on the X 1 Σ+
g electronic ground state rotational series
and fundamenal vibrational tones in molecular hydrogen. In combination with recent accurate ab initio calculations, we
demonstrate systematic tests of quantum electrodynamical (QED) effects in molecules. Moreover, the precise comparison
between theory and experiment can provide stringent constraints on possible new interactions that extend beyond the
Standard Model.
a E.
J. Salumbides, G. D. Dickenson, T. I. Ivanov and W. Ubachs, Phys. Rev. Lett. 107, 043005 (2011).
115
MG. RADICALS AND IONS
MONDAY, JUNE 17, 2013 – 1:30 PM
Chair: CHRISTOPHER NEESE, The Ohio State University, Columbus OH
MG01
15 min 1:30
COMBINATION BANDS BETWEEN 2900 AND 3600 CM
−1
OF CYCLIC O4 CATION TRAPPED IN SOLID NEON
The infrared spectrum of cyc-O4 + trapped in solid neon includes a group of combination bands built on (ν 1 + ν 5 ) of groundstate cyc-O4 + . Each peak lies close to a counterpart previously reporteda in a study of the infrared laser photodissociation
spectroscopy of a mass-selected molecular beam. This agreement is consistent with the vibrational assignment of three
low-frequency modes of cyc-O4 + that was proposed in the earlier study. The spectra obtained for the isotopologues formed
by the substitution of one or two 18 O2 moieties suggest the occurrence of interaction with a nearby excited electronic state.
a A.
M. Ricks, G. E. Douberly, and M. A. Duncan, Int. J. Mass Spectrom. 283, 69 (2009).
MG02
15 min 1:47
FOURIER TRANSFORM FAR-INFRARED SPECTROSCOPY OF
CHROTRON SOLEIL
HN+
2
ON THE AILES BEAMLINE OF SYN-
O. PIRALIa , S. GRUETa , M. VERVLOET, Ligne AILES, Synchrotron SOLEIL, L’Orme des Merisiers SaintAubin, 91192 Gif sur Yvette Cedex - France.
We report the pure rotation spectrum of HN+
2 measured by Fourier Transform (FT) absorption spectroscopy in the 20-40
cm−1 spectral range. The cations are produced in a liquid nitrogen cooled hollow cathode discharge cell developed on
the AILES beamline of synchrotron SOLEIL. The set-up was optimized by recording rotation-vibration spectra of H+
3 (ν2
−1
+
−1
(ν
band
centered
at
3234
cm
)
and
HCO
(ν
band
centered
at
3089
cm
).
Many
band centered at 2521 cm−1 ), HN+
1
1
2
rotation-vibration lines have been assigned for each ion and 5 pure rotational transitions have been detected for HN+
2.
These results demonstrate the feasibility to record far-infrared (far-IR) spectra of cationic species using FT broad band
spectroscopy associated to the bright synchrotron radiation continuum as an alternative to laser-based frequency tunable
techniques. In the presentation, we will describe the experimental set-up, the results obtained and the perspectives of this
preliminary work which will rely on the exploitation of intense Coherent Synchrotron Radiation (CSR).
a Also
116
MG03
15 min 2:04
SUB-DOPPLER SPECTROSCOPY OF ND3 H ION IN THE NH STRETCHING MODE
+
CHIH-HSUAN CHANG, GRANT T. BUCKINGHAM , and DAVID J. NESBITT, JILA, National Institute of
+
Despite early successes with velocity modulation spectroscopya,b of ammonium (NH+
4 ) and perdeuteroammonium (ND4 )
+
cation, corresponding studies of any of the mixed H/D isotopomers (NHm D4−m ) have proven elusive. In this talk, we
present first high resolution results on the lone NH stretch fundamental mode for the jet cooled ND3 H+ ion, based on
tunable IR difference frequency absorption spectroscopy in a slit jet, sub-Doppler resolution infrared spectrometer. Supersonically cooled ND3 H+ ions are generated by modulated (50 KHz) discharges (650V, 500 mA) in ND3 doped H2 /Ne slit
jet expansions, monitored by time-gated, lock-in detection methods and with absorption sensitivities near the quantum shot
noise limit. Jet cooled (30 K) P , Q, and R branch rovibrational progressions in the a-type NH stretch band are observed
and unambiguously assigned by four line ground state combination differences, with additional confirmation by nuclear
spin statistical weights for the 3 identical D atoms (I = 1). Least squares fits to this parallel band yield precision rotational
constants and an NH stretch vibrational band origin at 3316.8347(19) cm−1 . These high resolution spectroscopic results
prove to be in generally excellent agreement with high level ab initio theoretical predictions by Martin and Leec .
a Mark.W.
Crofton, Takeshi. Oka, J. Chem. Phys. 86, 5983, (1987).
Schafer, M. H. Begemann, C. S. Gudeman, R. J. Saykally, J. Chem. Phys. 79, 3159, (1983).
c Jan. M. L. Martin, Timothy J. Lee, Chem. Phys. Lett. 258, 129 (1996)
b E.
MG04
15 min 2:21
INFRARED SPECTROSCOPY OF JET COOLED ND2 H+
2
MOLECULAR IONS: THE SYMMETRIC AND ANTISYM-
METRIC NH STRETCH MODES
CHIH-HSUAN CHANG and DAVID J NESBITT, JILA, National Institute of Standards and Technology University of Colorado, and Department of Chemistry and Biochemistry University of Colorado at Boulder, Colorado 80309.
Rovibrational progressions in the symmetric (v 6 ) and antisymmetric (v 1 ) NH stretching modes of the ND2 H+
2 molecular
ion are observed for the first time, exploiting the i) high ion density and ii) high resolution capabilities of our slit jet discharge infrared spectrometer. These isotopomeric ions are generated by striking a modulated (50 KHz) electrical discharge
in a mixture of ND3 /H2 O/H2 gases, achieving a modulated ion density suitable for time-gated, lock-in detection in the
throat of a long path slit-jet expansion. Assignment of both b-type and c-type bands enables high accuracy determination of the rotational constants (A′′ =4.85598(19), B ′′ =3.96811(11), and C ′′ =3.44661(40) cm−1 ), with band origins for v 1
and v 6 modes determined to be 3297.54367(34) and 3337.90456(33) cm−1 , respectively. The results prove to be in good
agreement with anharmonically corrected predictions from ab initio quartic force fields of Martin and Leea .
a Jan.
M. L. Martin and Timothy J. Lee, Chem. Phys. Lett. 258, 129 (1996)
MG05
15 min 2:38
PRECISION LASER SPECTROSCOPY OF
H+
3
HSUAN-CHEN CHEN, Institute of Photonics Technologies, National Tsing Hua University, Hsinchu 30013,
Taiwan; JIN-LONG PENG, Center for Measurement Standards, Industrial Technology Research Institute,
Hsinchu 30011, Taiwan; T. AMANO, Department of Chemistry and Department of Physics and Astronomy,
University of Waterloo, Waterloo, ON N2L 3G1, Canada; JOW-TSONG SHY, Institute of Photonics Technologies, National Tsing Hua University and Department of Physics, National Tsing Hua University, Hsinchu
30013, Taiwan.
The high-resolution sub-Doppler Lamb dips of the ν2 fundamental band transitions of H+
3 have been observed using an
extended negative glow discharge tube as an ion source and a periodically poled lithium niobate optical parametric oscillator
as a radiation source.a The absolute frequencies of five transitions were measured to an accuracy of 250 kHz using a fiber
optical frequency comb. In addition, we measured the homogeneous linewidths of these lines. Physical significance of
these results will be discussed in terms of collisional processes.
a H.-C.
Chen, C.-Y. Hsiao, J.-L. Peng, T. Amano, and J.-T. Shy, Phys. Rev. Lett., 109, 263002 (2012)
117
MG06
SUB-DOPPLER SPECTROSCOPY OF
15 min 2:55
H+
3
JAMES N. HODGES, ADAM J. PERRY, BRIAN M. SILLER, Department of Chemistry, University of Illinois, Urbana, IL 61801; BENJAMIN J. MCCALL, Departments of Chemistry, Astronomy, and Physics, University of Illinois, Urbana, IL 61801.
Spectroscopy of H+
3 is of fundamental interest for advancing ab initio efforts to calculate spectra with high precision and
accuracy. H+
3 is the simplest polyatomic ion, which is why it is an excellent benchmark for theory. In order to perform
calculations with spectroscopic accuracy, relativistic and non-adiabatic corrections to the Born-Oppenhiemer approximation must be included; calculations with these considerations agree to within hundredths of a wavenumber.a Increasing
the precision of the calculations further will require a treatment of quantum electrodynamic effects, as has already been
implemented for the diatomic case,b and testing these calculations will require higher-precision experimental data to guide
ab initio calculations.
Noise Immune Cavity Enhanced Optical Heterodyne Velocity Modulation Spectroscopy, or NICE-OHVMScd , is a highly
sensitive, highly precise technique that we have employed to observe transitions in the ν2 fundamental band of H+
3 . It
combines the advantages of cavity enhancement and heterodyne detection with the ion-neutral discrimination afforded
by velocity modulation. Combining a cavity with a high power mid-infrared light source, we can saturate rovibrational
transitions. The resulting Lamb dips may be fit in order to determine line centers to a much higher precision than is
possible for ordinary Doppler broadened profiles. Additionally, a frequency comb is used to surpass the limited accuracy
and precision of a wavemeter. Here we present the results from comb calibrated H+
3 transitions observed via NICEOHVMS. Precision and accuracy of ∼ 1 MHz were achieved representing the most accurate and precise H+
3 line list that
has been obtained to date.
a O.
L. Polyansky, J. Tennyson, J. Chem. Phys. (1999), 110, 5056–5064.
Komasa, et al. J. Chem. Theor. Comp. (2011), 7, 3105–3115.
c B. M. Siller, et al. Opt. Express (2011), 19, 24822–7.
d K. N. Crabtree, et al. Chem. Phys. Lett. (2012), 551, 1–6.
b J.
MG07
HIGH PRECISION SPECTROSCOPY OF
15 min 3:12
CH+
5
USING NICE-OHVMS
JAMES N. HODGES, ADAM J. PERRY, Department of Chemistry, University of Illinois, Urbana, IL 61801;
BENJAMIN J. MCCALL, Departments of Chemistry, Astronomy, and Physics, University of Illinois, Urbana,
IL 61801.
The elusive methonium ion, CH+
5 , is of great interest due to its highly fluxional nature. The only published high-resolution
infrared spectrum remains completely unassigned to this date.a The primary challenge in understanding the CH+
5 spectrum
is that traditional spectroscopic approaches rely on a molecule having only small (or even large) amplitude motions about
a well-defined reference geometry, and this is not the case with CH+
5.
We are in the process of re-scanning Oka’s spectrum, in the original Black Widow discharge cell, using the new technique
of Noise Immune Cavity Enhanced Optical Heterodyne Velocity Modulation Spectroscopy (NICE-OHVMS).bc The high
precision afforded by optical saturation in conjunction with a frequency comb allows transition line centers to be determined
with sub-MHz accuracy and precision – a substantial improvement over the 90 MHz precision of Oka’s work.
With a high-precision linelist in hand, we plan to search for four line combination differences to directly determine the
spacings between rotational energy levels. Such a search is currently infeasible due to the large number of false positives
resulting from the relatively low precision and high spectral density of Oka’s spectrum. The resulting combination differences, in conjunction with state-of-the-art theoretical calculations from Tucker Carrington,d may provide the first insight
into the rotational structure of this unique molecular system.
a E.
T. White, J. Tang, T. Oka, Science (1999) 284, 135–137.
M. Siller, et al. Opt. Express (2011), 19, 24822–24827.
c K. N. Crabtree, et al. Chem. Phys. Lett. (2012), 551, 1–6.
d X. Wang, T. Carrington, J. Chem. Phys., (2008), 129, 234102.
b B.
118
MG08
15 min 3:29
INFRARED SPECTROSCOPY OF THE MASS 43 CATION: ACETYL CATION AND PROTONATED KETENE
The mass 43 cation [C2 , H3 , O]+ is prominent in mass spectra of organic molecules. Theory predicts no less than nine
structural isomers, and the acetyl cation CH3 CO+ is the global minimum. The infrared spectrum of the mass 43 cation
from methyl acetate shows vibrations only from the acetyl cation. The effects of the methyl free internal rotor are discussed.
The mass 43 cation from acetone shows evidence for both the acetyl cation and the less thermodynamically stable ( 50
kcal/mol) protonated ketene isomer CH2 COH + . The effects of varying the kinetic trapping conditions in our ion source
on isomeric ratios of the mass 43 cation are discussed.
MG09
15 min 3:46
UBIQUITOUS INTERSTELLAR MOLECULES WITH RADICALLY DIFFERENT CATION STRUCTURES: INFRARED SPECTROSCOPY OF FORMALDEHYDE AND METHANOL CATIONS
Formaldehyde and methanol are detected in interstellar and circumstellar sources by rotational transitions resulting from
their well-known structures. For the radical cations with nominal formulas [C, H2 , O]+ and [C, H4 , O]+ , no such measurements have been made in interstellar sources or in the laboratory to our knowledge. We measured the infrared spectrum
of both radical cations in the gas phase using infrared photodissociation spectroscopy and found structures that differ
drastically from the neutral closed shell species. For the case of [C, H2 , O]+ , formaldehyde cation CH2 O+ and hydroxymethylene cation CHOH + are predicted to be minima with only 5 kcal/mol difference in stability. We see evidence for
two isomers in the infrared spectrum and investigate the effects of the argon tag on these small (four atoms) radical cations.
For the mass 32 cation [C, H4 , O]+ , theory predicts the methyleneoxonium cation CH2 OH2+ to be about 15 kcal/mol more
stable than the methanol cation CH3 OH + . We present definitive assignments of vibrational features to these two isomers
of the mass 32 cation. We discuss the kinetic trapping occurring in the ion source that produce the thermodynamically
unfavorable CH3 OH + simultaneously with the lowest energy structure, CH2 OH2+ . The application of our findings to
astrochemistry is discussed.
Intermission
MG10
15 min 4:15
THE CORONENE VIBRONIC STATES ABOVE THE FIRST IONIZATION POTENTIAL INVESTIGATED THROUGH
TPEPICO EXPERIMENTS
PH. BRECHIGNAC, C. FALVO, P. PARNEIX , T. PINO, O. PIRALI, Institut des Sciences Moléculaires
d’Orsay, CNRS UMR8214, Univ Paris-Sud, Bât 210, F91405 Orsay Cedex, France; G. GARCIA, L. NAHON,
Synchrotron SOLEIL, L’ Orme des Merisiers, St Aubin, B.P. 48, 91192 Gif sur Yvette, France; C. JOBLIN,
D. KOKKIN, A. BONAMMY, IRAP, Université de Toulouse [UPS], CNRS, Toulouse, France; G. MULAS,
INAF-Osservatorio Astronomico di Cagliari-Astrochemistry Group, Strada 54, Località Poggio dei Pini, I09012 Capoterra (CA), Italy.
Threshold Photoelectron spectra (TPES), as well as Total Ion Yeld (TIY) spectra of jet-cooled Coronene (C12 H24 ) have
been obtained using the electron/ion coincidence imaging spectrometer DELICIOUS IIa available at the DESIRS beamline
of the French Synchrotron facility SOLEIL. The obtained data can be interpreted in the light of new theoretical DFT and
TDDFT based calculations. They will be discussed in comparison to available photoelectron (PES) and optical absorption
data. New autoionizing neutral states have also been observed and their relaxation to final cationic states characterized.
a G.A.
Garcia, H. Soldi-Lose, and L. Nahon, Rev. Sci. Instrum. 80, 023102 (2009).
119
MG11
MASS ANALYZED THRESHOLD IONIZATION OF LUTETIUM DIMER
15 min 4:32
LU WU, MOURAD ROUDJANE, YANG LIU AND DONG-SHENG YANG, Department of Chemistry, University of Kentucky, Lexington, KY 40506-0055.
Lu2 is produced in a pulsed laser-vaporization metal-cluster source and studied by mass-analyzed threshold ionization
(MATI) spectroscopy. The MATI spectrum displays several long progressions from the transitions between various vibrational levels of the neutral and ion electronic states. From the spectrum, the upper limit of the ionization energy of
the dimer is determined to be 43996 cm−1 , and the vibrational frequencies are measured to be 121 cm−1 in the neutral
state and 90 cm−1 in the ion state. By combining with ab initio calculations at CASPT2 level, the ground state of Lu2 is
3 −
2
1
1
2
identified as 3 Σ−
g . The Σg state has an electron configuration of 6sσg 5dπu 5dπu 6sσu , which is formed by the interactions
2
2
of two Lu atoms in the D(5d6s ) ground state. Ionization of the neutral state removes a 5dπ u bonding electron and yields
a ion state with a considerably longer bond distance. Lu2 has a very different bonding feature from La2 , for which a 1 Σ+
g
ground state was previously identified with an electron configuration of 5dπu4 6sσg2 formed by the interactions of two La
atoms in the 4 F(5d2 6s) excited state.a
a Yang
Liu, Lu Wu, Chang-Hua Zhang, Serge A. Krasnokutski, and Dong-Sheng Yang, J. Chem. Phys. 135, 034309 (2011).
MG12
C-C BOND ACTIVATION AND COUPLING OF PROPENE INDUCED BY LA ATOM
15 min 4:49
DILRUKSHI HEWAGE, Department of Chemistry, University of Kentucky, Lexington, KY 40506-0055;
HONG TAO, Department of Chemistry, Southwest Forestry University, Kunming 650224, PR China;
RUCHIRA SILVA, SUDESH KUMARI, AND DONG-SHENG YANG, Department of Chemistry, University of Kentucky, Lexington, KY 40506-0055.
A series of La(Cn Hm ) complexes with n ≤ 6 and m ≤ 12 were produced by the reactions between propene and La in
a supersonic molecular beam source. Their formation and structures were investigated using mass-analyzed threshold
ionization (MATI) spectroscopy in combination with theoretical calculations. Previously, we identified the formation of
La(C3 H4 ) and H-La(C3 H5 ) through dehydrogenation and metal insertion mechanisms. In this work, we will discuss the
formation of La(CH2 ) and La(C4 H6 ) by La induced C-C bond activation and coupling. La(CH2 ) is formed by the C-C
bond breakage and 1,2-hydride shift of propene and is a Schrock-type carbene complex. This complex is then coupled with
the C=C bond of a second propene molecule to form La(C4 H6 ) by removing two hydrogen atoms. The resultant La(C4 H6 )
complex was idetified in two low-energy isomeric forms: one was a metallacycle (isomer A) and the other was lanthanum
trimethylenemethane (isomer B). Both La(C4 H6 ) isomers are in a doublet ground state, with isomer A in Cs point group
and isomer B in C3v . Adiabatic ionization energies and several vibrational frequencies of the two complexes were obtained
from the sharp MATI spectra.
120
MG13
HIGH-RESOLUTION PHOTOELECTRON SPECTROSCOPY OF 2-BUTYNE
15 min 5:06
UGO JACOVELLA, BÉRENGER GANS and FRÉDÉRIC MERKT, ETH Zürich, Laboratorium für
Physikalische Chemie, Wolfgang-Pauli-Strasse 10, 8093 Zürich, Switzerland.
Using a coherent narrow-band vacuum-ultraviolet (VUV) laser source (bandwitdh of 0.008 cm−1 )a coupled to a photoionization and pulse-field-ionization zero-kinetic-energy photoelectron (PFI-ZEKE) spectrometer, the threshold photoionization of polyatomic molecules can be studied at high resolution.
We present a new measurement of the PFI-ZEKE photoelectron spectrum of the origin band of the X+ 2 E2(d) ← X 1 A1(s)
ionizing transition of 2-butyne at a resolution of 0.15 cm−1 . Despite this high resolution, the spectral congestion originating from the combined effects of the internal rotation, the spin-orbit coupling and the Jahn-Teller effect prevented the
full resolution of the rotational structure of the photoelectron spectrum. Combined with the known structure of the X
1
A1(s) ground state of 2-butyne, including the free internal rotationbcd , the spectrum was used to derive information on the
X+ 2 E2(d) ground state of the 2-butyne radical cation. The rotational branch structure of the spectrum points at a complex
energy-level structure of the cation and at the importance of a shape resonance enhancing g photoelectron partial wavese .
a U.
Hollenstein, H. Palm, and F. Merkt, Rev. Sci. Instrum. 71, 4023 (2000).
C. Longuet-Higgins Mol. Phys. 6, 445 (1963).
c J. T. Hougen J. Chem. Phys. 37, 1433 (1962).
d P. R. Bunker Mol. Phys. 8, 81 (1964).
e H. Xu, U. Jacovella, B. Ruscic, S. T. Pratt and R. R. Lucchese J. Chem. Phys. 136, 154303 (2012).
b H.
MG14
15 min 5:23
UNDERSTANDING COMPLEX SPECTRAL SIGNATURES OF EMBEDDED EXCESS PROTONS IN MOLECULAR
SCAFFOLDS WITH THIRD ORDER CORRECTIONS TO THE HARMONIC POTENTIAL SURFACE
ANDREW F. DEBLASE and MARK A. JOHNSON, Yale University, P.O. Box 208107, New Haven, CT
06520, USA; THOMAS LECTKA, Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218, USA; XUN WANG and KENNETH D. JORDAN, University of Pittsburgh, 219 Parkman Avenue,
Pittsburgh, PA 15260, USA; ANNE B. McCOY, The Ohio State University, Columbus, Ohio 43210, USA.
Overtones and combination bands observed in vibrational predissociation spectra of cold ions can often be anticipated
by expanding the potential energy surface to third order. This is achieved by relating the third derivatives to the matrix
elements that couple the allowed and forbidden states in the harmonic basis. Such a strategy has been successful in
predicting Fermi resonances in formic acid clusters and some charged H-bonded complexes. Furthermore, third order
couplings have been used to develop a vibrational adiabatic model in which excitation of a bright state is distributed over
a Franck-Condon envelop of a lower energy mode, such as a water rocking against triatomic domains of molecular anions.
Previous applications include the analysis of long vibrational progressions of soft modes in the OH stretching region of the
actetate-water binary complex. Here we explore to extent to which this order of correction captures the irregular patterns
associated with intramolecular proton bonds.
MG15
SLOW ELECTRON VELOCITY-MAP IMAGING OF La2 (C6 H6 ) AND La(C6 H6 )2
15 min 5:40
RUCHIRA SILVA AND DONG-SHENG YANG, Department of Chemistry, University of Kentucky, Lexington, KY 40506-0055.
Slow electron velocity-map imaging (SEVI) was used to study the structures and electronic states of La2 (C6 H6 ) and
La(C6 H6 )2 complexes formed in a metal cluster beam source. Electron spectra obtained from SEVI have the energy
resolution of ∆E/eKE ≈ 2% at eKE=400cm−1. The SEVI technique offers much higher data collection efficiency than
pulsed-field ionization zero electron kinetic energy spectroscopy. From the SEVI spectra, adiabatic ionization energies
were measured to be 32141(5) cm−1 for La2 (C6 H6 ) and 39033(5) cm−1 for La(C6 H6 )2 . The most active vibrational
transition for both complexes was identified to be a metal-ligand stretching mode with a frequency of 180 cm−1 in the ion
state. In addition, a benzene ring out-of-plane deformation mode was measured to be 303 cm−1 for [La2 (C6 H6 )]+ and 408
cm−1 for [La(C6 H6 )2 ]+ . By combining the spectra with theoretical calculations, we identified the 2 Ag ←1 Ag transition of
La2 (C6 H6 ) (C2h ) and 3 A←2 A of La(C6 H6 )2 (C1 ). By measuring the anisotropy parameter (β) from photoelectron angular
distribution, we found that the outgoing electron was from a largely La 6s-based molecular orbital in both complexes.
121
MG16
15 min 5:57
INFRARED SPECTROSCOPY AND STRUCTURES OF MASS-SELECTED RHODIUM CARBONYL AND
RHODIUM DINITROGEN CATIONS
HEATHER L. ABBOTT, Department of Chemistry and Biochemistry, Kennesaw State University, Kennesaw,
GA 30144; ANTONIO D. BRATHWAITE and MICHAEL A. DUNCAN, Department of Chemistry, University of Georgia, Athens, GA 30602-2256.
+
Rhodium carbonyl cations, Rh(CO)+
n , and rhodium dinitrogen cations, Rh(N2 )n , are produced by laser vaporization in a
pulsed-nozzle molecular beam source. Mass-selected infrared photodissociation spectroscopy of these ions and their argon
tagged analogs are compared to density functional theory computations. Structures of the rhodium cations are determined
based upon the number, frequency position and relative intensity of the infrared active bands between 2000 and 2400
cm−1 . Computed binding energies and fragmentation patterns suggest that four carbonyl ligands bind strongly to the
central rhodium cation.
122
MH. MICROWAVE
MONDAY, JUNE 17, 2013 – 1:30 PM
Chair: ELANGANNAN ARUNAN, Indian Institute of Science, Bangalore, India
MH01
THE PROTOTYPE DIPEPTIDE GLY-GLY: A ROTATIONAL STUDY
15 min 1:30
M. VARELA, C. CABEZAS, S. MATA, J. L. ALONSO, Grupo de Espectroscopía Molecular (GEM), Edificio
47011 Valladolid, Spain.
The simplest dipeptide Gly-Gly has been examined for the first time in the gas phase by laser ablation molecular beam
Fourier transform microwave (LA-MB-FTMW) spectroscopy. The nuclear quadrupole hyperfine structure of two 14 N
nuclei has been totally resolved allowing the conclusive identification of three conformers in the supersonic expansion.
Intramolecular hydrogen bonding interactions have been analyzed on the bases of the structure of the observed conformers.
Present results indicate that it is possible to face the study larger peptides using LA-MB-FTMW spectroscopy.
MH02
15 min 1:47
GAS-PHASE STRUCTURES OF LINALOOL AND COUMARIN STUDIED BY MICROWAVE SPECTROSCOPY
H. V. L. NGUYEN, W. STAHL, Institut für Physikalische Chemie, RWTH Aachen University, Landoltweg 2,
52074 Aachen, Germany; and J.-U. GRABOW, Institut für Physikalische Chemie und Elektrochemie, Lehrgebiet A, Callinstrasse 3-3a, 30167 Hannover, Germany.
The microwave spectra of two natural substances, linalool and coumarin, were recorded in the microwave range from 9 to
16 GHz and 8.5 to 10.5 GHz, respectively.
Linalool is an acyclic monoterpene and the main component of lavender oil. It has a structure with many possible conformations. The geometry of the lowest energy conformer has been determined by a combination of microwave spectroscopy
and quantum chemical calculations. Surprisingly, a globular rather than a prolate shape was found. This structure is probably stabilized by a π interaction between two double bonds which are arranged in two stacked layers of atoms within
the molecule. A-E splittings due to the internal rotation of one methyl group could be resolved and the barrier to internal
rotation was determined to be 400.20(64) cm−1 . The standard deviation of the fit was close to experimental accuracy. For
an identification of the observed conformer not only the rotational constants but also the internal rotation parameters of one
of the methyl groups were needed.
Coumarin is a widely used flavor in perfumery as sweet woodruff scent. The aromatic structure allows solely for one
planar conformer, which was found under molecular beam conditions and compared to other molecules with similar structures. Here, the rotational spectrum could be described by a set of parameters including the rotational constants and the
centrifugal distortion constants using a semi-rigid molecule Hamiltonian. Furthermore, the rotational transitions of all nine
13
C isotopologues were measured in natural abundance. As a consequence, the microwave structure of coumarin could be
almost completely determined.
123
MH03
MW SYSTEMATIC STUDY OF ALKALOIDS: THE DISTORTED TROPANE OF SCOPOLINE
10 min 2:04
PATRICIA ECIJA, EMILIO J. COCINERO, FRANCISCO J. BASTERRETXEA, JOSÉ A. FERNANDEZ,
FERNANDO CASTANO, Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Ap.644, E-48940, Bilbao, Spain; ALBERTO LESARRI, Departamento de
Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, E-47011 Spain.
Tropane alkaloids have diverse pharmacological uses and are well-known for their neurostimulant activity. Previous
structure-activity-relationship established correlations between bioactivity and several aspects of ligand conformation and
stereochemistry, including delicate intramolecular effects like nitrogen inversiona. We have initiated a series of structural
studies on tropane alkaloidsb , aimed to discerning their intrinsic stereochemical properties using rotational spectroscopy in
supersonic jetsc . Here we extend these studies to the epoxytropanes, initially motivated to interrogate the influence of the
epoxy group on nitrogen inversion and ring conformation. The rotational spectrum evidences a single structure in the gas
phase, providing a first description of the (three ring) structurally-distorted tropane in scopoline. The determined rotational
parameters of scopoline reveal the structural consequences of the intramolecular cyclation of scopine, which breaks the
original epoxy group and creates a new ether bridge and a 7β-hydroxytropane configuration. The hydroxyl group further
stabilizes the molecule by an O − H · · · N intramolecular hydrogen bond, which, in turn, forces the N-methyl group to
the less stable axial formb . The experimental work was supported by ab initio and DFT calculations.
i) S.Singh, Chem. Rev. 100, 925 (2000); ii) A. Krunic, D. Pan, W.J. Dunn III, S.V.S. Miariappan, Bioorg. Med. Chem.
17, 811 (2009).
b
E.J. Cocinero, A. Lesarri, P. Écija, J.-U. Grabow, J.A. Fernández, F. Castaño, Phys. Chem. Chem. Phys. 12, 6076 (2010).
c
E.J. Cocinero, A. Lesarri, P. Écija, J.-U. Grabow, J.A. Fernández, F. Castaño, Phys. Chem. Chem. Phys. 12, 12486
(2010).
a
MH04
15 min 2:16
STRUCTURAL STUDIES OF PYRROLE-BENZENE COMPLEXES BY CHIRPED-PULSE ROTATIONAL SPECTROSCOPY
SIMON LOBSIGER, CRISTOBAL PEREZ, DANIEL P. ZALESKI, NATHAN A. SEIFERT,
BROOKS H. PATE, Department of Chemistry, University of Virginia, McCormick Rd., Charlottesville,
VA 22904; CHANTAL PFAFFEN, MARIA A. TRACHSEL, SAMUEL LEUTWYLER, Departement für
Chemie und Biochemie, Universität Bern, Freiestrasse 3, 3012 Bern, Switzerland.
Non-covalent intermolecular interactions are important in structural biology. The N-H · · · π hydrogen bond between
amino acid side chains is an important structural determinant and highly affects the secondary structure of proteins. The
pyrrole-benzene complex can be viewed as a model system for studying these fundamental interactions. Previous IR and
UV spectroscopic studies of the pyrrole-benzene complex by Dauster et al.a and Pfaffen et al.b support a T-shaped structure
with an N-H · · · π hydrogen bond to the benzene ring.
In order to obtain accurate structural information we have investigated the broadband rotational spectrum of the supersonicjet cooled complexes of pyrrole with benzene and benzene-d1 in the 2-18 GHz frequency range. In addition to the hetero
dimer we have also observed the two cyclic mixed trimers (pyrrole)2-benzene and pyrrole-(benzene)2.
a I.
Dauster, C. A. Rice, P. Zielke, and M. A. Suhm Phys. Chem. Chem. Phys. 10, 2827 (2008)
Pfaffen, D. Infanger, P. Ottiger, H. M. Frey, and S. Leutwyler Phys. Chem. Chem. Phys. 13, 14110 (2011)
b C.
124
MH05
15 min 2:33
A “WET DOG" TUNNELING MOTION AS THE CAUSE FOR THE DOUBLED ROTATIONAL SPECTRUM OF 1IODONONAFLUOROBUTANE
W. C. BAILEY, Chemistry-Physics Department (Retired), Kean University, Union, New Jersey, USA 07083;
R. K. BOHN, Departments of Chemistry and Physics, University of Connecticut,Storrs, Connecticut, 062693060, USA.; G. S. GRUBBS II, Department of Chemistry, Wesleyan University, Hall-Atwater Laboratories,
52 Lawn Ave, Middletown, Connecticut, 06459-0180, USA.; Z. KISIEL, Institute of Physics, Polish Academy
of Sciences, Al. Lotnikóv 32146, 02-668 Warszawa, Poland.; S. A. COOKE, School of Natural and Social
Sciences, Purchase College SUNY, 735 Anderson Hill Road, Purchase, NY 10577, USA.
A chirped pulse Fourier transform microwave spectrometer has been used to record
the rotational spectra of 1-iodononafluorobutane between 8 GHz and 12 GHz. The
target compound was spectroscopically examined as it participated in a supersonic
expansion of argon. The spectra recorded are dense owing in part to the small rotational constants, B + C ≈ 480 MHz, but also to hyperfine structure generated by the
coupling of angular momenta of the iodine nucleus and the rotating molecular frame,
e.g. | χab | ≈ 1200 MHz. Notably all of the hyperfine components were observed
as doublets. It is postulated that this doubling effect is the result of a low barrier,
double minimum potential between two mirror image transoid structures. The tunneling motion between these structures resembles that of a “wet dog" shaking itself dry. Numerous transitions are shifted in
frequency and it is proposed that the density of rotational energy levels from the two interacting states results in numerous
perturbations to the energy levels involved. A preliminary spectral analysis of over 400 transitions will be presented, along
with the results of supporting quantum mechanical calculations.
MH06
15 min 2:50
TORSIONAL SPLITTING IN THE ROTATIONAL SPECTRUM FROM 8 TO 650 GHz OF THE GROUND STATE OF
1,1-DIFLUOROACETONE
L. MARGULÈS, R. A. MOTIYENKO, Laboratoire de Physique des Lasers, Atomes, et Molécules, UMR
CNRS 8523, Université de Lille I, 59655 Villeneuve d’Ascq Cedex, France; P. GRONER, Department of
Chemistry, University of Missouri-Kansas City, 5100 Rockhill Road, Kansas City, MO 64110-2499, USA;
F. De CHIRICO, A. TURK, S. A. COOKE, School of Natural and Social Sciences, Purchase College SUNY,
735 Anderson Hill Road, Purchase, NY 10577, USA.
Measurements on the rotational spectrum of 1,1-difluoroacetone have been extended
from the cm-wave region into the mm-wave region. Measurements between 150 GHz
and 600 GHz were performed at Lille at room temperature. About 2000 transitions have
been added to the known line listing for the ground statea . The range of J and K−1
values, for both the A and E torsional substates, now span 1 - 60 and 0 - 30, respectively. Analysis of the cm-wave spectrum was only possible using the Watson S-reduced
Hamiltonian, with the A-reduction producing a poor spectral fit. For that analysis only
quartic centrifugal distortion terms were required. With the newly recorded higher J
and K−1 measurements it is necessary to expand the Hamiltonian to now include sextic
and octic centrifugal distortion terms. This should allow us to extend the assignment to even higher J and K−1 and perhaps
to shed more light into failure of the A-reduction Hamiltonian to achieve a satisfactory fit for the cm-wave transitions. The
effective barrier to methyl group internal rotation has been determined more accurately.
a G.
S. Grubbs II, P. Groner, S. E. Novick and S. A. Cooke J. Mol. Spectrosc. 280 21-26, 2012.
125
MH07
15 min 3:07
AN IMPROVED ANALYSIS OF THE SEVOFLURANE-BENZENE STRUCTURE BY CHIRPED PULSE FTMW
SPECTROSCOPY
País Vasco (UPV/EHU), Campus de Leioa, Ap. 644, E-48080 Bilbao, Spain; ISABELLE KLEINER, Laboratorie Interuniversitaire des Systèmes Atmosphériques (LISA), CNRS et Universités Paris Est et Paris Diderot,
61. av Général de Gaulle, 94010 Créteil, France.
Recent improvements to the 2-8 GHz CP-FTMW spectrometer at University of Virginia have improved the structural and
spectroscopic analysis of the sevoflurane-benzene cluster. Previously reported resultsa , although robust, were limited to a
fit of the a-type transitions of the normal species in the determination of the six-fold barrier to benzene internal rotation.
Structural analysis was limited to the benzene hydrogen atom positions using benzene-d1. The increased sensitivity of
the new 2-8 GHz setup allows for a full internal rotation analysis of the a- and c-type transitions of the normal species,
which was performed with BELGI. A fit value for V6 of 32.868(11) cm−1 is determined. Additionally, a full substitution
structure of the benzene carbon atom positions was determined in natural abundance. Also, new measurements of a
sevoflurane/benzene-d1 mixture enabled detection of 33 of the 60 possible 2 D / 13 C double isotopologues. This abundance
of isotopic data, a total of 45 isotopologues, enabled a full heavy atom least-squares r0 structure fit for the complex,
including positions for all seven fluorines in sevoflurane.
a N. A. Seifert, D. P. Zaleski, J. L. Neill, B. H. Pate, A. Lesarri, M. Vallejo, E. J. Cocinero, F. Castańo. 67th OSU Int. Symp. On Mol. Spectrosc.,
Columbus, OH, 2012, MH13.
MH08
10 min 3:24
STRUCTURE DETERMINATION OF TWO STEREOISOMERS OF SEVOFLURANE DIMER BY CHIRPED PULSE
FTMW SPECTROSCOPY
País Vasco (UPV/EHU), Campus de Leioa, Ap. 644, E-48080 Bilbao, Spain.
Two stereoisomers of sevoflurane dimer have been detected using chirped pulse FTMW spectroscopy from 2-8 GHz. The
identified complexes are distinguished by their differing helicities, and together both isomers form a diastereomeric pair,
one being homochiral (RR/SS) and the other heterochiral (RS/SR). For both isomers, all 8 13 C isotopologues have been
assigned, and two 18 O isotopologues have also been detected for the homochiral isomer, for a total of 18 isotopologues.
MP2/6-311++g(d,p) calculations predict the heterochiral isomer as 1.2 kJ mol−1 above the homochiral species, which is
consistent with the observed relative intensities between the two species. A summary of these microwave results, including
a comparison between the Kraitchman and ab initio structures, will be presented.
Intermission
126
MH09
THE COMPLETE MOLECULAR GEOMETRY OF SALICYL ALDEHYDE FROM ROTATIONAL
SPECTROSCOPY
15 min 3:50
O. DOROSH, E. BIALKOWSKA-JAWORSKA, Z. KISIEL, L. PSZCZOLKOWSKI, Institute of Physics, Polish Academy of Sciences, Al. Lotników 32/46, 02-668 Warszawa, Poland; M. KANSKA, T. M. KRYGOWSKI,
Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warszawa, Poland; H. MAEDER, Institut für Physikalische Chemie, Christian-Albrechts-Universität zu Kiel, Olshausenstrasse 40, D-24098 Kiel,
Germany.
Salicyl aldehyde is a well known planar molecule containing an internal hydrogen bond. In preparing the publication of our
previous report of the study of its rotational spectruma we have taken the opportunity to update the structure determination
of this molecule to the complete reSE geometry. The molecule contains 15 atoms and we have used supersonic expansion
FTMW spectroscopy to obtain rotational constants for a total 26 different isotopic species, including all singly substitued
species relative to the parent molecule. The 13 C and 18 O substitutions were measured in natural abundance, while deuterium substitutions were carried out synthetically. The reSE determination requires the calculation of vibration-rotation
changes in rotational constants from an ab initio anharmonic force field, which necessitates some compromises in the
level of calculation for a molecule of the size of salicyl aldehyde. For this reason we studied the five lowest vibrationally
excited states, by using the combination of room-temperature mm-wave spectroscopy and waveguide Fourier transform
cm-wave spectroscopy. The experimental excited state rotational constants were then used to calibrate the anharmonic
force field calculation. The resulting reSE geometry is compared with other types of geometry determination possible from
this data, with emphasis on the effect of the near zero principal coordinate of the important C2 atom.
a Z.Kisiel
et al., 61st OSU Symposium on Molecular Spectroscopy, The Ohio State University, Ohio 2006, RI-12.
MH10
10 min 4:07
LABORATORY OBSERVATION OF THE ROTATIONAL SPECTRUM OF A POTENTIAL INTERSTELLAR SUGAR,
ERYTHROSE
I. PENA, C. CABEZAS, A. M. DALY, S. MATA, J. L. ALONSO, Grupo de Espectroscopía Molecular (GEM),
The rotational spectrum of erythrose has been recorded in the frequency region 6 – 12 GHz using a chirped-pulse Fourier
transform microwave spectrometer (CP-FTMW)a combined with a laser ablation (LA) source.b The investigation of rotational spectra of erythrose is of astrophysical and biological relevance. However, no gas-phase data were available on
erythrose. It is syrup at room temperature and vaporization using conventional methods leads to decomposition. A non convetional laser ablation method has been successfully used to vaporize erythrose and two cyclic forms have been observed
using rotational spectroscopy. α-erythrose has been found to have rotational constants are A = 2586.8998 (21) MHz,
B = 2353.0837 (41) MHz and C = 1773.2378 (18) MHz and β-erythrose is characterized with rotational constants
A = 3109.2005 (46) MHz, B = 1856.1298 (15) MHz, C = 1616.5557 (18) MHz.
a G.
b S.
G. Brown, B. C. Dian, K. O. Douglass, S. M. Geyer, S. T. Shipman, B. H. Pate, Rev. Sci. Instrum. 2008, 79, 053103.
Mata, I. Peña, C. Cabezas, J. C. López, J. L. Alonso, J. Mol. Spectrosc. 2012, 280, 91.
127
MH11
15 min 4:19
ALDOPENTOSES IN THE GAS PHASE: ROTATIONAL SPECTRA OF D-XYLOSE, D-ARABINOSE, D-LYXOSE
AND 2-DEOXY-D-RIBOSE
I. PENA, C. CABEZAS, A. M. DALY, C. BERMUDEZ, S. MATA, S. BLANCO, J. C. LOPEZ,
J. L. ALONSO, Grupo de Espectroscopía Molecular (GEM), Edificio Quifima, Laboratorios de Espectroscopía y Bioespectroscopía, Parque Científico, Universidad de Valladolid, 47011 Valladolid, Spain.
A new experimental approach chirped-pulse Fourier transform microwave (CP-FTMW) spectrometer combined with a
laser ablation (LA) sourcea,b has been used to investigate the conformational distribution of aldopentoses. From their laser
ablated crystalline solids, two conformers of α-D-xylopyranose, four of β-D-arabinopyranose, five of β-D-lyxopyranose
and two α- and four β- of 2-deoxy-D -ribopyranose have been identified in the supersonic jet on the basis of the experimental rotational constants extracted from the analysis of the spectra. The five monosubstituted 13 C species of the most
abundant conformer of D-xylopyranose have been observed in their natural abundance, taking advantage of the sensitivity
of our spectrometer. The anomeric effect and cooperative hydrogen bonding have been found to be the main factors which
control the conformational behavior of the observed conformers.
a G.
b S.
MH12
A ROTATIONAL STUDY OF D-MANNOSE AND D-GALACTOSE
15 min 4:36
I. PENA, A. M. DALY, C. CABEZAS, S. MATA, J. L. ALONSO, Grupo de Espectroscopía Molecular
The rotational spectrum of two aldohexoses, D-mannose and D-galactose, has been investigated in the 6 – 12 GHz frequency range by means of a combination of laser ablation and broadband Fourier transform microwave spectroscopy
(CP-FTMW).a, b Five conformers of α-D-mannopyranose and two of α-D-galactopyranose, showing the 4 C1 ring configuration, have been identified from the rotational constants in conjunction with ab initio computations. Stabilization
factors, which include stereolectronic effects, such as anomeric effect or gauche effect, and the network of clockwise or
anticlockwise hydrogen bonds have been analyzed in terms of the observed conformers.
a G.
b S.
MH13
UNVEILING THE SWEET CONFORMATIONS OF KETOHEXOSES
15 min 4:53
C. BERMUDEZ, I. PENA, C. CABEZAS, A. M. DALY, S. MATA, J. L. ALONSO, Grupo de Espectroscopía
Molecular (GEM), Edificio Quifima, Laboratorios de Espectroscopía y Bioespectroscopía, Parque Científico,
Universidad de Valladolid, 47011 Valladolid, Spain.
The conformational behavior of ketohexoses D-Fructose, L-Sorbose, D-Tagatose and D-Psicose has been revealed from
their rotational spectra. A broadband microwave spectrometer (CP-FTMW)a combined with a laser ablation (LA) sourceb
has been used to rapidly acquire the rotational spectra in the 6 to 12 GHz frequency range. All observed species are stabilized by complicated intramolecular hydrogen-bonding networks. Structural motifs related to the sweetness of ketohexoses
are revealed.
a G.
b S.
128
MH14
15 min 5:10
ELUCIDATING THE STRUCTURE OF SUGARS: MW SPECTROSCOPY COMBINED WITH ULTRAFAST UV LASER VAPORIZATION
EMILIO J. COCINERO, PATRICIA ECIJA, FRANCISCO J. BASTERRETXEA, JOSÉ A. FERNANDEZ,
FERNANDO CASTANO, Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV-EHU), Ap. 644, E-48080 Bilbao, Spain; ALBERTO LESARRI, Departamento
de Química-Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, E-47011 Spain;
JENS-UWE GRABOW, Institut für Physikalische Chemie, Lehrgebiet A, Universität Hannover, Callinstraße.
3A, D-30167 Hannover, Germany; ALVARO CIMAS, Laboratoire Analyse et Modélisation pour la Biologie
et l’Environnement, Université d’Évry val d’Essonne, F-91025 Evry (France).
Carbohydrates are one of the most versatile biochemical building blocks, widely acting in energetic, structural or recognition processes. Even the small monosaccharides display unique structural and conformational freedom and may coexist in
many open-chain or cyclic forms. We recently initiated the investigation of a series of monosaccharides using a combination of ultrafast laser vaporization and microwave spectroscopy in supersonic jet expansions. We present several structural
studies on carbohydrates of aldosesa and ketosesb of five and six carbon sugars vaporized by UV ultrafast laser vaporization
and stabilized in a jet expansion. The experimental evidence confirms that sugars exhibits a α-/β-pyranose conformation
(6-membered ring), sharply contrasting with the furanose form (5-membered ring) found in the nature (as component of
RNA, sucrose). In addition, thanks to the use of enriched samples, we have experimentally determined the substitution
and effective structures. Finally, the structure of several monosaccharides was compared and common structural patterns
of their conformational landscape will be showed.
a
E. J. Cocinero, A. Lesarri, P. Écija, F. J. Basterretxea, J. U. Grabow, J. A. Fernández and F. Castaño Angew. Chem. Int. Ed. 51, 3119-3124, 2012.
E. J. Cocinero, A. Lesarri, P. Écija, Á. Cimas, B. G. Davis, F. J. Basterretxea, J. A. Fernández and F. Castaño J. Am. Chem. Soc. 135, 2845-2852,
2013.
b
MH15
15 min 5:27
TOWARDS SOLVATION OF A CHIRAL ALPHA-HYDROXY ESTER: BROADBAND CHIRP AND NARROW BAND
CAVITY FOUIRIER TRANSFORM MICROWAVE SPECTROSCOPY OF METHYL LACTATE-WATER CLUSTERS
JAVIX THOMAS, OLEKSANDR SUKHORUKOV, WOLFGANG JAEGER, YUNJIE XU, Department of
Chemistry, University of Alberta, Edmonton, AB, T6G 2G2, Canada.
Methyl lactate (ML), a chiral alpha-hydroxy ester, has attracted much attention as a prototype system in studies of chirality
transfer,[1] solvation effects on chiroptical signatures,[2] and chirality recognition.[3] It has multiple functional groups
which can serve both as a hydrogen donor and acceptor. By applying rotational spectroscopy and high level ab initio
calculations, we examine the delicate competition between inter- and intramolecular hydrogen-bonding in the ML-water
clusters. Broadband rotational spectra obtained with a chirp Fourier transform microwave (FTMW) spectrometer, reveal
that the insertion conformations are the most favourable ones in the binary and ternary solvated complexes. In the insertion
conformations, the water molecule(s) inserts itself (themselves) into the existing intramolecular hydrogen-bonded
ring formed between the alcoholic hydroxyl group and the oxygen of the carbonyl group of ML. The final frequency
measurements have been carried out using a cavity based FTMW instrument where internal rotation splittings due to the
ester methyl group have also been detected. A number of insertion conformers with subtle structural differences for both
the binary and ternary complexes have been identified theoretically. The interconversion dynamics of these conformers
and the identification of the most favorable conformers will be discussed.
1. C. Merten, Y. Xu, Angew. Chem. Int. Ed., 2013, 52, 2073 –2076.
2. M. Losada, Y. Xu, Phys. Chem. Chem. Phys., 2007, 9, 3127-3135; Y. Liu, G. Yang, M. Losada, Y. Xu, J. Chem. Phys.,
2010, 132, 234513/1-11.
3. A. Zehnacker, M. Suhm, Angew. Chem. Int. Ed. 2008, 47, 6970 - 6992.
129
MI. ELECTRONIC
MONDAY, JUNE 17, 2013 – 1:30 PM
Chair: DAMIEN FORTHOMME, Brookhaven National Lab, Upton, NY
MI01
15 min 1:30
A DPF ANALYSIS YIELDS QUANTUM MECHANICALLY ACCURATE ANALYTIC POTENTIAL ENERGY FUNCTIONS FOR THE A 1 Σ+ and X 1 Σ+ STATES OF NaH
ROBERT J. LE ROY, SADRU WALJI, KATHERINE SENTJENS, Department of Chemistry, University of
Waterloo, Waterloo, Ontario N2L 3G1, Canada.
Alkali hydride diatomic molecules have long been the object of spectroscopic studies.a However, their small reduced mass
makes them species for which the conventional semiclassical-based methods of analysis tend to have the largest errors. To
date, the only quantum-mechanically accurate direct-potential-fit (DPF) analysis for one of these molecules was the one
for LiH reported by Coxon and Dickinson.b The present paper extends this level of analysis to NaH, and reports a DPF
analysis of all available spectroscopic data for the A 1 Σ+ − X 1 Σ+ system of NaH which yields analytic potential energy
functions for these two states that account for those data (on average) to within the experimental uncertainties.
a W.C.
b
Stwalley, W.T. Zemke and S.C. Yang, J. Phys. Chem. Ref. Data 20, 153-187 (1991).
J.A. Coxon and C.S. Dickinson, J. Chem. Phys. 121, 8378 (2004).
MI02
15 min 1:47
UNCERTAINTIES IN PROPERTIES CALCULATED FROM FITTED POTENTIAL FUNCTIONS and DETERMINING
POTENTIAL FUNCTIONS FROM FITS TO BOUND → CONTINUUM INTENSITY DATA
ROBERT J. LE ROY, Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1,
Canada.
In recent years it has become increasingly common to analyse spectroscopic data by using “direct potential fits" of simulated data generated from analytic potential energy functions to experiment to optimize the parameters defining that
potential energy function. This has the advantages of circumventing use of the semiclassical approximations associated
with traditional methodologies, and of directly yielding a closed-form expression that is the most compact and comprehensive way to summarize what we know about a molecule. A question which then arises is: What are the uncertainties in
properties computed using this potential? It turns out that this question is very closely related to the question of how to apply this simulation/fitting method efficiently to the analysis of bound → continuum intensity data. Both depend upon being
able to answer the question: What are the partial derivatives of a wavefunction with respect to the parameters defining the
potential energy function from which it is generated? It will be shown that such partial derivatives may be obtained readily
as the ‘particular’ solutions of linear inhomogeneous differential equations of a type that is routinely solved in another
context for calculating the centrifugal distortion constants of diatomic molecules.a,b Applications of this technique have
been incorporated into the publicly available bound-state data analysis and simulation program DPotFit and the distributed
bound → continuum simulation/fitting program BCONT. c
a
J.M. Hutson, J. Phys. B (At. Mol. Phys) 14, 851 (1981).
J. Tellinghuisen, J. Mol. Spectrosc. 122, 455 (1987).
c See http://leroy.uwaterloo.ca/programs/.
b
130
MI03
15 min 2:04
ASSIGNING COMPLEX VIBRATION-TUNNELING SPECTRA USING FRANCK-CONDON FINGERPRINTS
EDUARDO BERRIOS, PRAVEEN SUNDARADEVAN and MARTIN GRUEBELE, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Il 61801.
We propose Franck-Condon fingerprinting as a method to assign complex vibration-tunneling spectra. The B̃ electronic
excited state of Thiophosgene (SCCl2 ) is our prototype case. Assignment of its spectrum has proven to be difficult
because large tunneling splittings and near-degenerate vibrational frequencies. The dispersed fluorescence spectrum of
each unkown vibration-tunneling state reveals its wavefunction character onto the known SCCl2 vibrational progressions
in the ground states. This Franck-Condon fingerprint allows us to assign several vibration-tunneling states of SCCl2 in
the B̃ electronic excited state. These assigned transitions could be fitted by an effective vibration-tunneling Hamiltonian
within measurement uncertainty.
MI04
15 min 2:21
OPTICAL-OPTICAL DOUBLE RESONANCE AND LIF SPECTROSCOPY OF THE JET-COOLED BORON CARBIDE (BC) FREE RADICAL
FUMIE X. SUNAHORI, RAMYA NAGARAJAN, AND DENNIS J. CLOUTHIER, Department of Chemistry,
University of Kentucky, Lexington, KY 40506-0055.
The boron carbide (11 BC and 10 BC) free radical has been produced in a pulsed discharge jet using a precursor mixture
of 1% trimethylborane [B(CH3 )3 ] in high pressure argon. The 560 nm B4 Σ− - X 4 Σ− electronic transition of both isotopologues has been studied in detail by LIF and emission spectroscopy. The 290 nm E4 Π - X 4 Σ− band system was
also studied using high-resolution LIF techniques, although the rotational structure of the bands was found to be quite
complicated due to significant spin-spin and spin-orbit splittings in the excited state. In order to fully assign the spectra,
an optical-optical double resonance (OODR) scheme was implemented in which a yellow-green dye laser beam populated
a specific rotational level of the B state and a second tunable red dye laser beam was used to promote the E4 Π - B4 Σ−
transition. The OODR transitions were detected by monitoring the resulting E4 Π - X 4 Σ− UV fluorescence. The OODR
spectra consist of readily assignable spin-split P-, Q-, and R-branch lines from a single intermediate state N value, which
greatly facilitated the assignment of the E - X LIF spectra. Progress in analyzing the spectra will be discussed.
MI05
10 min 2:38
REINVESTIGATION OF THE EMISSION SPECTRA FOLLOWING THE 266 NM PHOTOLYSIS OF
IODOMETHANES
CIAN-PING TU, HSIN-I CHENG, and BOR-CHEN CHANG, Department of Chemistry, National Central
University, 300 Jhongda Road, Jhongli 32001, Taiwan.
Nascent emission spectra following the 266 nm photolysis of iodomethanes (CHI3 , CH2 I2 , CH3 I, and CH2 ICl) were
recorded in a slow flow system, and are similar to those following the 266 nm photolysis of bromomethanesa except a
number of unknown bands that appear between 520 nm and 820 nm. Interestingly, there are no isotopic shifts in these
unknown bands even when the precursors were replaced by the deuterated or 13 C-substituted isotopomers (CD2 I2 , CD3 I,
and 13 CH2 I2 ).b This indicates that the carrier of these unknown bands does not contain any hydrogen or carbon atoms.
Laser-induced fluorescence (LIF) excitation and dispersed-fluorescence (DF) spectra were recorded, but these spectra show
different vibrational structures than those of the unknown bands. While the LIF and DF spectra can be well described by
1 +
the I2 b3 Π+
0,u −X Σg transition, there exist systematic deviations between the unknown bands and the I2 b−X transition.
We have improved the signal-to-noise (S/N) ratios and the resolution for these unknown bands. Our new analysis shows
that the unknown bands consist of several band systems including the I2 b−X transition. Moreover, the excited state iodine
atom was found in the nascent emission spectra, but its formation mechanism still remains unsolved. The details of our
current progress will be presented.
a S.-X.
b J.-J.
Yang, G.-Y. Hou, J.-H. Dai, C-.H. Chang, and B.-C. Chang, J. Phys. Chem. A 114, 4785 (2010).
Du, C.-H. Chen, and B.-C. Chang, 67th OSU International Symposium on Molecular Spectroscopy, WG04 (2012).
131
MI06
15 min 2:50
CAVITY RINGDOWN ABSORPTION SPECTRUM OF THE T1 (n, π ) ← S0 TRANSITION OF
2-CYCLOHEXEN-1-ONE
∗
KATHERINE L. ZABRONSKY, MICHAEL O. McANALLY, DANIEL J. STUPCA, NATHAN R. PILLSBURY, and STEPHEN DRUCKER, Department of Chemistry, University of Wisconsin-Eau Claire, Eau
Claire, WI 54702.
The cavity ringdown (CRD) absorption spectrum of 2-cyclohexen-1-one (CHO) was recorded over the range 401.5–410.5
nm in a room-temperature gas cell. The very weak band system (ǫ ≤ 0.02 dm3 mol−1 cm−1 ) in this region is due to the
T1 (n, π*) ← S0 electronic transition. The 000 origin band was assigned to the feature observed at 24,558.6 ±0.3 cm−1 .
We have assigned about 25 vibronic transitions in a region extending from −200 to +350 cm−1 relative to the origin band.
From these assignments we determined fundamental frequencies for several vibrational modes in the T1 excited state. The
table below compares their frequencies to corresponding values measured for CHO vapor in the S0 electronic ground state
(via far-IR spectroscopy)a and the S1 (n, π*) excited state (via near-UV CRD spectroscopy).b
Mode
39
38
37
36
Low-frequency fundamentals (cm−1 ) of CHO∗ vapor
Description
S0
S1 (n, π ) T1 (n, π ∗ )
ring twist
99.2
122.1
99.5
bend (inversion of C-5)
247
251.9
253.2
C=C twist
304.1
303.3
247.8
C=O wag
485
343.9
345.5
For ν39 and ν37 , the differences between S1 and T1 frequencies are noteworthy. These differences suggest that the electron
delocalization associated with the π ∗ ← n chromophore in CHO is substantially different for singlet vs. triplet excitation.
a T.
L. Smithson and H. Wieser, J. Chem. Phys. 73, 2518 (1980); M. Z. M. Rishard and J. Laane, J. Molec. Struct. 976, 56 (2010).
Z. M. Rishard, E. A. Brown, L. K. Ausman, S. Drucker and J. Laane, J. Phys. Chem. A 112, 38 (2008).
b M.
MI07
15 min 3:07
COMPUTATIONAL INVESTIGATION OF THE T1 (n, π ) STATE OF 2-CYCLOHEXEN-1-ONE
∗
MICHAEL O. McANALLY and STEPHEN DRUCKER, Department of Chemistry, University of WisconsinEau Claire, Eau Claire, WI 54702.
We have used several computational methods, including TDDFT and EOM–EE–CCSD, to determine the equilibrium geometry and harmonic vibrational frequencies of 2-cyclohexen-1-one (CHO) in its T1 (n, π ∗ ) excited state. Atom displacement vectors for the normal modes indicate that the lowest-frequency vibration, ν39 , is best described as a ring-twisting
motion, whereas ν38 is a ring-bending vibration consisting mainly of C-5 displacement toward and away from the plane in
which the other heavy atoms lie. These updated descriptions are transposed with respect to those in the previous literature.a
The table below shows that the EOM–EE–CCSD harmonic frequencies generally agree well with fundamentals obtained
spectroscopically.b In particular, the ν39 frequency determined by EOM–EE–CCSD is more accurate than the TDB3LYP
result, with errors of +2% and +20%, respectively. This outcome is traceable in part to a larger ν39 reduced mass calculated
by EOM–EE–CCSD, stemming from a less planar O=C–C=C dihedral angle (170.4◦ via EOM–EE–CCSD vs. 177.4◦ via
TDB3LYP).
Low-frequency fundamentals (cm−1 ) for CHO in its T1 (n, π ∗ ) state
Mode
Description
TDB3LYP/cc-pVTZ EOM–EE–CCSD/cc-pVDZ Experimentb
39
ring twist
119.6
101.4
99.5
38
bend (inversion of C-5)
255.9
272.0
253.2
37
C=C twist
306.9
223.0
247.8
36
C=O wag
359.0
340.2
345.5
The success of EOM–EE–CCSD in this application could be due to its ability to describe multiconfigurational wavefunctions within a single-reference formalism.
a T. L. Smithson and H. Wieser, J. Chem. Phys. 73, 2518 (1980); M. Z. M. Rishard, E. A. Brown, L. K. Ausman, S. Drucker, J. Choo, and J. Laane,
J. Phys. Chem. A 112, 38 (2008).
b Previous talk.
Intermission
132
MI08
15 min 3:40
PROBING COMPETITIVE NONCOVALENT INTERACTIONS: RESONANCE ENHANCED TWO-PHOTON IONIZATION (R2PI) SPECTROSCOPY OF HALOAROMATIC CLUSTERS
SILVER NYAMBO, LLOYD MUZANGWA, BRANDON UHLER AND SCOTT A. REID, Department of
Chemistry, Marquette University, Milwaukee, WI 53233.
Non-covalent interactions in bromobenzene have been studied here using resonance two-photon ionization (R2PI) spectroscopy combined with a linear TOF-mass spectrometer. Bromobenzene clusters were created in a supersonic expansion
with helium as a carrier gas. The molecules were excited and ionized from the ground state in a two stage process. The
general trend observed in the R2PI spectra of all the clusters is the broadness and a red-shift relative to the monomer
absorption. Optimized dimer and trimer structures were calculated at the M06-2x/aug-cc-pVDZ level, which show that
π-stacked and C-H/π interactions are most important in these clusters. TD-DFT calculations of the different cluster conformers have been carried out to assess the geometry changes active upon electronic excitation. The theoretical studies are
helpful in explaining trends observed in the R2PI spectra.
MI09
NONLINEAR DUAL-COMB SPECTROSCOPY WITH TWO-PHOTON EXCITATION
15 min 3:57
S. A. MEEK, A. HIPKE, T. W. HÄNSCH, N. PICQUÉ, Max-Planck-Institut für Quantenoptik, HansKopfermann-Straße 1, D-85748 Garching, Germany.
Dual frequency comb spectroscopy has proven to be a powerful method for acquiring broadband, high resolution spectra
with measurement times that are much shorter than in traditional moving-mirror Fourier transform spectroscopy. Because
the measurements are carried out with femtosecond lasers, this technique has great potential for decreasing the measurement times and improving the signal-to-noise ratio of nonlinear spectroscopic measurements, such as two-photon excitation
or Raman processes. In the case of two-photon excitation, an entire spectrum can be obtained at a given signal level using
dual-comb spectroscopy in the same time that a measurement of a single transition frequency would be obtained with a
continuous laser of the same average power.
In this presentation, I will show the latest results in extending the dual-comb technique to two-photon excitation spectroscopy, with measurements on gas-phase rubidium and liquid-phase dye samples. In our realization of dual-comb spectroscopy, two frequency combs with slightly different repetition rates are combined on a beam splitter and directed into a
sample, and we measure the intensity of the resulting fluorescence as a function of time. Because of the different repetition
rates, the time delay between a pulse from the first comb and the next pulse from the second comb changes linearly with
time, simulating the action of the moving mirror in a traditional Michelson interferometer. The Fourier transform of the
measured time-domain interferogram produces a radio-frequency spectrum that can be directly converted to a broadband
optical spectrum through a linear scaling of the frequency. To achieve the highest possible resolution, it is necessary to
compensate the residual relative fluctuations of the repetition rate and the carrier-envelope offset frequency of the frequency
combs. Measuring RF beatnotes of each comb with two CW lasers provides two error signals that can be used to correct
the recorded interferograms. This correction is applied differently for one-photon and two-photon spectra, providing a
method of distinguishing the two.
133
MI10
15 min 4:14
NEW DEVELOPMENTS OF BROADBAND CAVITY ENHANCED SPECTROSCOPIC TECHNIQUES
A. WALSH, D. ZHAO, H. LINNARTZ, Sackler Laboratory for Astrophysics, Leiden Observatory, University
of Leiden, P.O. Box 9513, NL-2300 RA Leiden, the Netherlands; W. UBACHS, LaserLaB, VU University
Amsterdam, De Boelelaan 1081, NL-1081 HV, Amsterdam, The Netherlands.
In recent years, cavity enhanced spectroscopic techniques, such as cavity ring-down spectroscopy (CRDS), cavity enhanced
absorption spectroscopy (CEAS), and broadband cavity enhanced absorption spectroscopy (BBCEAS), have been widely
employed as ultra-sensitive methods for the measurement of weak absorptions and in the real-time detection of trace
species. In this contribution, we introduce two new cavity enhanced spectroscopic concepts:
a) Optomechanical shutter modulated BBCEAS,a a variant of BBCEAS capable of measuring optical absorption in pulsed
systems with typically low duty cycles. In conventional BBCEAS applications, the latter substantially reduces the signalto-noise ratio (S/N), consequently also reducing the detection sensitivity. To overcome this, we incorporate a fast optomechanical shutter as a time gate, modulating the detection scheme of BBCEAS and increasing the effective duty cycle
reaches a value close to unity. This extends the applications of BBCEAS into pulsed samples and also in time-resolved
studies.
b) Cavity enhanced self-absorption spectroscopy (CESAS),b a new spectroscopic concept capable of studying light emitting
matter (plasma, flames, combustion samples) simultaneously in absorption and emission. In CESAS, a sample (plasma,
flame or combustion source) is located in an optically stable cavity consisting of two high reflectivity mirrors, and here it
acts both as light source and absorbing medium. A high detection sensitivity of weak absorption is reached without the
need of an external light source, such as a laser or broadband lamp. The performance is illustrated by the first CESAS
result on a supersonically expanding hydrocarbon plasma.c We expect CESAS to become a generally applicable analytical
tool for real time and in situ diagnostics.
a A.
Walsh, D. Zhao, W. Ubachs, H. Linnartz, J. Phys. Chem. A, dx.doi.org/10.1021/jp310392n, in press, 2013.
Walsh, D. Zhao, H. Linnartz Rev. Sci. Instrum. 84(2), 021608 2013.
c A. Walsh, D. Zhao, H. Linnartz Appl. Phys. Lett. 101(9), 091111 2012.
b A.
MI11
15 min 4:31
MEASURING THE QUENCHING OF NO FLUORESCENCE PRODUCED FROM THE EXCITATION OF PHOTOFRAGMENTED NITROBENZENE USING A PICOSECOND LASER.
The military is interested in using spectroscopic methods to detect nitroaromatic compounds related to explosives. Upon
absorption of a UV photon, nitrobenzene can dissociate into C6 H5 O and NO. Wynn, et al. a have shown that looking at
NO fluorescence from the photodissociated nitrobenzene could be a possible detection method. However, the fluorescence
can easily be quenched by molecular oxygen and other constituents in air. We have measured fluorescence lifetimes of
the nascent NO resulting from photo-fragmented nitrobenzene using a pulsed picosecond tunable laser (pulse width ≈15
ps) by means of a two-color process. In the two-color process, photons of a particular energy dissociated the nitrobenzene
while photons of a different energy probed the A2 Σ+ ← X 2 Π(1/2,3/2) NO band system between 225-260 nm. We have
performed the measurements with different background pressures of He, N2 , and air. We present the results of these
measurements which indicate considerable quenching of the NO fluorescence due to oxygen.
a Wynn,
C. M.; Palmacci, S.; Kunz, R. R.; and Rothschild, M.Opt. Express, OSA, 2010, 18, 5399-5406
134
MI12
SPECTROSCOPY OF LUMINESCENT CRYSTALS CONTAINING RARE EARTH ELEMENTS
15 min 4:48
MENG-LING CHEN, KWANG-HWA LII, and BOR-CHEN CHANG, Department of Chemistry, National
Central University, 300 Jhongda Road, Jhongli 32001, Taiwan.
We have studied the spectroscopy of luminescent crystals containing rare earth elements such as KEuGe2 O6 ,a
Cs3 EuSi6 O15 ,b K4 [(UO2 )Eu2 (Ge2 O7 )2 ], and R2 (C8 H10 O4 )3 (R= Y, Tb, or Eu). The emission and excitation spectra
of these compounds were recorded at ambient temperature. These spectra are consistent with the structures which were
determined by single crystal X-ray diffraction. Crystals containing hybrid luminescent centers were also synthesized and
interesting energy transfer mechanisms were observed. For example, dramatic luminescence quenching was found in
KEux Nd1−x Ge2 O6 (x= 0.98, 0.96, 0.94, and 0.84) as well as in Cs3 Eu0.98 Nd0.02 Si6 O15 , while different compositions
of Yx Euy Tb2−x−y (C8 H10 O4 )3 exhibit different emission colors. Emission lifetimes were also measured for these compounds, and the results shed light on the energy transfer mechanisms. Detailed results of our research will be presented.
a P.-L.
Chen, P.-Y. Chiang, H.-C. Yeh, B.-C. Chang, and K.-H. Lii, Dalton Trans., 1721 (2008).
Hung, Y.-H. Chen, B.-C. Chang, and K.-H. Lii, Chem. Mater. 17, 5743 (2005).
b M.-Y.
MI13
DNA-ENHANCED DYE-SENSITIZED SOLAR CELLS
15 min 5:05
MARVIN POLLUM and CARLOS E. CRESPO-HERNÁNDEZ, Department of Chemistry and Center for
Chemical Dynamics, Case Western Reserve University, Cleveland, Ohio 44106.
Dye-sensitized solar cells (DSSCs) are a promising alternative to the current silicon solar cell technologies. DSSCs have
a lower manufacturing cost, can be made to be flexible, semi-transparent, and in any variety of colors for aesthetic applications. Despite these advantageous properties, the stability and power conversion efficiency of DSSCs are still lacking.
Recently, we have shown that the adsorption of DNA onto the semiconductor surface of a typical DSSC improves its
overall performance. Structure-function analysis, in conjunction with steady-state and time-resolved spectroscopic studies,
are currently being done to understand this phenomenon and to uncover the mechanism by which DNA boosts the overall
performance of DSSCs. This new knowledge is expected to facilitate the rational design of DSSCs that exhibit higher
power conversion efficiency than those currently available.
MI14
15 min 5:22
SIMULATION OF FREE→FREE ABSORPTION SPECTRA AND THE CALCULATION OF INTERACTION POTENTIALS FOR ALKALI-RARE GAS ATOM PAIRS
J. DARBY HEWITT, THOMAS M. SPINKA, JASON. D. READLE, and J. GARY EDEN,
Laboratory for Optical Physics and Engineering
University of Illinois at Urbana Champaign
Champaign, IL 61820.
2 +
We have simulated free→free (X2 Σ+
1/2 →B Σ1/2 ) absorption spectra for alkali-rare gas pairs. By comparing simulation
results with experimental data, we have been able to iteratively determine the form for the B2 Σ+
1/2 interaction potential for
the system for a range in internuclear separation of 1.5–20 Å. Simulation methods will be presented, as will our results
pertaining to Cs-Ar.
135
MI15
SPECTROSCOPY OF 1,2-DIPHENYLETHANE-(H2O)n (n=1-3) CLUSTERS
15 min 5:39
JOSEPH R. GORD, EVAN G. BUCHANAN, PATRICK S. WALSH, and TIMOTHY S. ZWIER, Department
of Chemistry, Purdue University, West Lafayette. IN 47907.
1,2-diphenylethane (DPE) is a prototypical flexible bichromophore which forms two conformers in the gas phase having
close lying S1 and S2 states. Resonant ion-dip infrared (RIDIR) spectroscopy in the alkyl CH stretch region, 2800-3000
cm−1 , was used to assign the two observed isomers to gauche and anti structures having C2 and C2h symmetry similar
to those in butane.a In the present work, the ultraviolet and infrared spectroscopy of DPE-(H2 O)n (n=1-3) clusters has
been studied to understand how the ’solvent’ water molecules bind to this molecule with two phenyl rings, and how the
solvent binding perturbs the excited state behavior. RIDIR spectra in the OH stretch region (3350-3750 cm−1 ) show
that DPE-(H2 O)1 adopts a single conformation in which the water molecule bridges the two phenyl rings of the gauche
conformer, forming π H-bonds with both rings. DPE-(H2 O)2 forms two structures, in which a water dimer is bound to
either the gauche or anti DPE conformer. In the anti DPE-(H2 O)2 structure, the water dimer interacts primarily with one
phenyl ring, disrupting the symmetry of DPE enough that the S1 and S2 origins are localized, splitting the origins by
approximately 50 cm−1 . The development of these cluster structures with additional H2 O molecules, and the OH stretch
spectra of the clusters in the excited state(s) will also be discussed.
a E.
G. Buchanan, J. C. Dean, T. S. Zwier and E. L. Sibert, III J. Chem. Phys 2013, 138.
MI16
15 min 5:56
TROPOLONE COMPLEXES FORMED WITH AMPHOTERIC LIGANDS: STRUCTURE AND DYNAMICS AS
VIEWED ACROSS THE VIBRONIC LANDSCAPE
DEACON J. NEMCHICK, KATHRYN CHEW, and PATRICK H. VACCARO, Department of Chemistry, Yale
University, P.O. Box 20817, New Haven, CT 06520-8107 USA.
Owing to the presence of a finite potential barrier that adjoins hydroxylic (proton-donating) and ketonic (proton-accepting)
oxygen atom centers, tropolone (TrOH) long has served as a model system for the investigation of coherent (symmetrical)
proton-transfer events. Hydrogen-bound complexes formed by docking amphoteric species onto the TrOH substrate, such
as those involving formic acid [TrOH-(FA)n] and other simultaneous donor-acceptor ligands, have been generated under
supersonic free-jet expansion conditions. For binary adducts (n=1), quantum-chemical calculations predict two nearly
degenerate isomers that can be labeled as external (ligand attached to the seven-membered aromatic ring) and internal
(ligand bound to the O−H · · · O reaction site), where the latter cleft-bound form offers the tantalizing possibility of
undergoing a double proton-transfer process. A variety of spectroscopic probes build around the intense Ã1 B2 − X̃1 A1
(π ∗ ← π) near-ultraviolet absorption feature of bare tropolone have been enlisted to elucidate the binding motifs and
reaction pathways in complexes containing one or more amphoteric ligands, including vibrationally resolved schemes
based upon laser-induced fluorescence (LIF), dispersed fluorescence (DF), and fluorescence hole-burning (FHB) methods.
Structural and dynamical information gleaned from these experiments will be discussed in light of complementary ab initio
calculations.
136
MJ. ATMOSPHERIC SPECIES
MONDAY, JUNE 17, 2013 – 1:30 PM
Chair: CHRIS MCRAVEN, Brookhaven National Lab, Upton, NY
MJ01
WATER BROADENING OF OXYGEN
15 min 1:30
BRIAN J. DROUIN, VIVIENNE PAYNE, Jet Propulsion Laboratory, California Institute of Technology,
4800 Oak Grove Dr., Pasadena, CA 91109; ELI MLAWER, Atmospheric and Environmental Research, 131
Hartwell Avenue, Lexington, MA 02421.
A need for precise air-mass retrievals utilizing the near-infrared O2 A-band has motivated measurements of the waterbroadening in oxygen. Experimental challenges have resulted in very little water broadened oxygen data, especially in
the near-infrared where pressure broadened linewidth must compete with the relatively large thermal linewidth. Existing
water broadening dataa for the O2 A-band is of insufficient precision for application to the atmospheric data. Because
of the nature of scattering processes, it is believed that broadening parameters for O2 from one spectral region may be
transferable to other spectral regions - so we investigated the O2 60 GHz magnetic dipole Q branch which is also used
prominently in remote sensing. Atmospheric retrievals of air-mass and temperature that use the 60 GHz magnetic dipole Q
branch incorporate a water-broadening parameter that is scaled to self-broadened values, but there is only high temperature
data that directly supports this hypothesis.b We present precise O2 -H2 O broadening measurements for the magnetic dipole
Q-branch and the pure-rotational band, measured at room temperature with a Zeeman-modulated absorption cell and a
frequency-multiplier spectrometer. Here we will describe the apparatus and the measurement analysis. Inter-comparisons
of these and other O2 broadening data sets confirm the expectation of only minor band-to-band scaling of pressure broadening. The measurement provides a basis for fundamental parameterization of retrieval codes for the long-wavelength
atmospheric measurements. Finally, we encourage the application of these measurements for retrievals of air-mass via
remote sensing of the oxygen A-band.
a
E.M. Vess et al. J. Phys. Chem. A 116, 4069-4073 (2012).
b
G. Fanjoux et al. J. Chem. Phys. 101(2) 1061-1071 (1994).
MJ02
LINE PARAMETERS FOR THE OXYGEN A BAND
15 min 1:47
D. CHRIS BENNER, V. MALATHY DEVI, JIAJUN HOO, Department of Physics, College of William and
Mary, Williamsburg, VA; KEEYOON SUNG, Jet Propulsion Laboratory, California Institute of Technology,
Pasadena, CA; JOSEPH T. HODGES, DAVID A. LONG, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD; THINH BUI, PRIYANKA MILINDA RUPASINGHE,
MITCHIO OKUMURA, California Institute of Technology, Pasadena, CA.
Simulation of the oxygen A band to a level that is sufficient for accurate studies of the Earth’s atmosphere is complex in that
not only are Doppler and Lorentz broadening important, but also Dicke narrowing, pressure shifts, line mixing and speed
dependence. In addition all of these parameters except the speed dependence require temperature dependence parameters
as well. To measure all of the required line parameters with the multispectrum nonlinear least squares fitting technique,a
spectra were acquired by the Bruker IFS125-HR Fourier Transform Spectrometer at the Jet Propulsion Laboratory in
combination with various multpass cells, a cavity ring down spectrometer at NIST and a photoacoustic spectrometer at the
California Institute of Technology. The combination of the data from these three very different types of spectrometers in a
single simultaneous fit of the entire band enables the measurement of all of these quantities. The results to this point will
be summarized.b.
a D.
Chris Benner, C. P. Rinsland, V. M. Devi, M. A. H. Smith, and D. Atkins, JQSRT 1995;53:705-21.
for the work at William and Mary was provided by JPL and the NIST Greenhouse Gas Measurements and Climate Research Program. Part
of the research described in this paper was performed at the Jet Propulsion Laboratory, California Institute of Technology under contracts with National
Aeronautics and Space Administration. Support for the work at NIST was provided by at the NIST Greenhouse Gas Measurements and Climate Research
Program and an Innovations in Measurement Sciences (IMS) award.
b Support
137
MJ03
AIR-BROADENING AND SHIFT PARAMETERS IN THE ν3 BAND OF OZONE
15 min 2:04
M. A. H. SMITH, Science Directorate, NASA Langley Research Center, Hampton, VA 23681-2199;
V. MALATHY DEVI and D. CHRIS BENNER, Department of Physics, The College of William and Mary,
Williamsburg, VA 23187-8795.
Line parameter errors can contribute significantly to the total errors in retrievals of terrestrial atmospheric ozone concentration profiles using the strong 9.6-µm band, particularly for nadir-viewing experimentsa. Detailed knowledge of
the interfering ozone signal is also needed for retrievals of other atmospheric speciesb in this spectral region. We have
determined Lorentz air-broadening and pressure-induced shift coefficients along with their temperature dependences for a
number of transitions in the ν3 fundamental band of 16 O3 . These results were obtained by applying the multispectrum nonlinear least-squares fitting techniquec to a set of 31 high-resolution infrared absorption spectra of O3 previously recorded
at temperatures between 160 and 300 K with several different room-temperature and coolable sample cells at the McMathPierce Fourier transform spectrometer at the National Solar Observatory on Kitt Peak. We compare our results with other
available measurements and with the ozone line parameters in the 2008 HITRAN databased .
a J.
Worden et al., J. Geophys. Res. 109 (2004) 9308-9319.
Beer et al., Geophys. Res. Lett. 35 (2008) L09801.
c D. Chris Benner et al., JQSRT 53 (1995) 705-721.
d L. S. Rothman et al., JQSRT 110 (2009) 533-572.
b R.
MJ04
15 min 2:21
AIR-BROADENED LINE SHAPES IN THE 2ν3 R BRANCH OF
12
CH4 BETWEEN 6014 AND 6100 CM−1
V. MALATHY DEVI, D. CHRIS BENNER, Dept. of Physics, The College of William and Mary, Williamsburg, VA 23187; K. SUNG, L. R. BROWN, T. J. CRAWFORD, SHANSHAN YU, Jet Propulsion Laboratory,
California Institute of Technology, Pasadena, CA 91109; M. A. H. SMITH, Science Directorate, NASA Langley Research Center, Hampton, VA 23681; A. W. MANTZ, Dept. of Physics, Astronomy and Geophysics,
Complete and accurate information on line shape parameters of 2ν3 methane transitions for air broadening as a function
of temperature is critical not only for the correct interpretation of the observed atmospheric spectra but also for the development of a reliable theoretical model. For this reason, we obtained a series of high-resolution, high S/N spectra of
high-purity 12 CH4 and 12 CH4 broadened with dry air at temperatures in the 130 to 295 K range using the Bruker IFS
125HR Fourier transform spectrometer at JPL. Two absorption cells were used in the experiment, a White cell with path
length of 13 m for room temperature spectra and a 21 m Herriott cella for cold sample spectra. The 15 spectra used in
the analysis consisted of 3 low pressure (0.26 to 2.57 Torr) spectra with pure 12 CH4 and 12 air-broadened spectra with
total sample pressures of 79-805 Torr and volume mixing ratios of methane between 0.23 and 1%. A multispectrum leastsquares fitting techniqueb was employed to fit all 15 spectra simultaneously. Preliminary results for select R(J) manifolds
will be presented.c
a A.
W. Mantz, K. Sung, L. R. Brown, et al., abstract submitted to this Symposium.
C. Benner, C. P. Rinsland, V. Malathy Devi, M. A. H. Smith and D. Atkins, JQSRT 53 (1995) 705-721.
c Research described in this paper was performed at Connecticut College, the College of William and Mary, NASA Langley Research Center and
the Jet Propulsion Laboratory, California Institute of Technology, under contracts and cooperative agreements with the National Aeronautics and Space
Administration.
b D.
138
MJ05
15 min 2:38
LINE BROADENING PARAMETERS OF METHANE AT 6000 CM
−1
VICTOR GORSHELEV, ANNA SERDYUCHENKO, M.BUCHWITZ, J.BURROWS, Insitute of Environmental Physics, University of Bremen, Germany; NEIL HUMPAGE, J. REMEDIOS, Earth Observation Science Group, University of Leicester, UK.
Being one of the most important greenhouse gases, methane (CH4 ) is also modified by anthropogenic activity. Nowadays, it can be monitored globally from space on the long-term scale using combinations of different remote sensing
instruments. The critical point for the retrieval algorithms is the knowledge of the spectroscopic parameters. Although a
significant amount of spectroscopic data on CH4 is available, the information on the line parameters in mid infrared (MIR)
spectral region is inadequate for accurate remote sensing applications and there is a need for improved spectroscopic line
parameters.
We report on the improved spectroscopic line parameters for CH4 in the spectral regions used by SCIAMACHY and
TANSO instruments around 6000 cm−1 .
New data were obtained using high resolution absorption spectra of CH4 , perturbed by oxygen, nitrogen and air. Spectra
were measured using Fourier transform spectrometer in a broad range of total pressures from 2 to 1000 mbar and temperatures down to 196 K. Calculations of broadening parameters were performed using Reference Forward Model assuming
Voigt line profile within international collaboration between the Molecular Spectroscopy Laboratory in IUP Bremen, and
Earth Observation Science Group, University of Leicester, UK.
Accuracy of the new data matches the level of the demands of modern datasets and remote sensing. The new data were
compared with the data included in the latest HITRAN edition and other published works. Before release for the general
scientific community, the new data was tested on the TANSO and SCIAMACHY retrievals.
MJ06
EXAMINING CONTRIBUTIONS TO LINE SHAPES IN THE ν1 + ν3 BAND OF ACETYLENE
15 min 2:55
MATTHEW J. CICH, SALVATORE M. CAIOLA, STEPHEN W LEE, GARY V. LOPEZ, TREVOR J.
SEARSa , Department of Chemistry, Stony Brook University, Stony Brook, New York 11794; DAMIEN
FORTHOMME, C. P. MCRAVEN, GREGORY E. HALL, Department of Chemistry, Brookhaven National
Laboratory, Upton, New York 11973; A. W. MANTZ, Department of Physics, Astronomy, and Astrophysics,
Using an extended cavity diode laser locked to a frequency comb, line shapes in the ν1 + ν3 combination band of acetylene
have been studied. The frequency stability of this experiment produces high accuracy measurements that provide rigorous
tests of line shape theories. Measurements of the P(11) line shape were made for pure acetylene and acetylene-nitrogen
gas mixtures at a series of temperatures between 125 K and 296 K. Using the speed-dependent Voigt line shape model,
parameters were determined by fitting data for all temperatures and pressures in a single multispectrum analysis. The
resulting parameters successfully reproduce the measured line shapes and are valid for the acetylene-nitrogen system over
the range of temperatures studied and combined pressures of up to 1 atmosphere.
P(11) is isolated with respect to hot band transitions and neighboring transitions of the same band, but this is an unusual
case. To explore the effects of overlapping lines, the P(1) transition was measured in a series of pure acetylene measurements in a congested spectral region. Overlapping hot band lines of measurable intensities were modeled and line shape
paramters were simultaneously determined for these along with the P(1) line. Additionally, the effects of line mixing
between overlapping ν1 + ν3 lines were explored using an appropriate line mixing model.
Acknowledgments: Work at Brookhaven National Laboratory was carried out under Contract No. DE-AC02-98CH10886
with the U.S. Department of Energy and supported by its Office of Basic Energy Sciences, Division of Chemical Sciences,
Geosciences and Biosciences.
a also:
Intermission
139
MJ07
15 min 3:30
REFINEMENT OF THE ROBERT-BONAMY FORMALISM: TAKING INTO ACCOUNT OF CONTRIBUTIONS
FROM THE LINE COUPLING
Q. MA, NASA/Goddard Institute for Space Studies and Department of Applied Physics and Applied Mathematics, Columbia University, 2880 Broadway, New York, NY 10025; C. BOULET, Institut des Sciences
Moléculaires d’Orsay (ISMO); CNRS (UMR8214) et Université Paris-Sud Bât 350 Campusd’Orsay F-91405
FRANCE; R. H. TIPPING, Department of Physics and Astronomy, University of Alabama, Tuscaloosa, AL
35487.
The Robert-Bonamy (RB) formalism a contains several approximations whose applicability has not been thoroughly justified. One of them is that lines of interest are well separated. When these authors develop the formalism, they have relied
on this assumption twice. First, in calculating the spectral density F(ω), they have only considered the diagonal matrix
elements of the resolvent operator. Due to this simplification, effects from the line mixing are ignored. Second, when
they apply the linked cluster theorem to remove the cutoff, they have assumed that matrix elements of the operator exp(iS1 - S2 ) can be replaced by the exponential of the matrix elements of - iS1 - S2 . With this replacement, effects from the
line coupling are also ignored. Although both these two simplifications are relied on the same approximation, their validity
criterions are different and the latter is more stringent than the former. As a result, in many cases where the line mixing
becomes negligible, significant effects from the line coupling have been completely missed. In the present study, we have
developed a new method to evaluate the matrix elements of exp(- iS1 - S2 ) and have refined the RB formalism such that the
line coupling can be well taking into account. Our numerical calculations of the half-widths for Raman Q lines of the N2
- N2 pair have demonstrated that effects from the line coupling are important. In comparison with values derived from the
RB formalism, new calculated values for these lines are reduced significantly. A recent study on this system by Thibault et
al. b has shown that in comparison with measurements and the most accurate close coupling calculations, results derived
from the RB formalism are overestimated by a large amount. As a result, the refinement of the RB formalism goes in the
right direction and these new calculated half-widths become closer to the ”true” values.
a D.
b F.
Robert and J. Bonamy, J. Phys.(Paris), 40, 923 (1979).
Thibault et al., J.Q.S.R.T 113, 1887 (2012).
MJ08
UNDISCOVERED ERRORS OF VOIGT PROFILE BEYOND TINY W-SHAPED RESIDUALS
15 min 3:47
G. WAGNER, M. BIRK, DLR, D-82234 Wessling, Germany; S.A. CLOUGH, Clough Radiation Associates,
89 Hancock Street, Lexington, MA 02420, USA.
Stimulated by valleys being notoriously too deep in atmospheric spectra close to strong lines optically thick lines in laboratory water spectra in the ν2 region were investigated. These spectra were previously used to generate a new spectroscopic
databasea,b applying the Voigt line shape function in a least squares fitting procedure including non-opaque lines, only.
Surprisingly, applying the new spectroscopic data, lines were found to be modeled too narrow when saturated. Fitting the
Lorentz broadening parameters (fixing the accurately known intensities) of the opaque lines yielded 3-4% higher values
than in the database. The reason and consequences will be given in this paper.
a L.H.
b M.
Coudert, G. Wagner, M. Birk, Y.I. Baranov, W.J. Lafferty, J.M. Flaud, J. Mol. Spectrosc., 251, 339-57 (2008).
Birk, G. Wagner, Journal of Quantitative Spectroscopy and Radiative Transfer, 113, 889-928 (2011).
140
MJ09
WATER INTENSITIES: AB INITIO VS. EXPERIMENT
15 min 4:04
MANFRED BIRK , GEORG WAGNER, DLR, D-82234 Wessling, Germany; LORENZO LODI,
JONATHAN TENNYSON, Department of Physics and Astronomy, University College London, London
WC1E 6BT, UK.
Ab initio calculations of water intensities are becoming mature and are claimed to have 1% accuracy in most cases. Experimental intensities with 1% accuracy can be achieved with some care. An intercomparison ab initio vs. experiment
of water intensities for ν2 (H2 16 O, H2 18 O) and the 1 µm band will be given. Some brief information on the ab initio
calculation will be presented while the main focus will be on the experiment and corresponding data analysis. Most of the
data show agreement within 2% between ab initio and experiment but part of the data also show larger differences up to
8%. Some of the differences can be attributed to ab initio calculation errors while others originate from experiment. At
present experiments are important to validate ab initio but ab initio can be very useful in validating the experiment.
MJ10
FT-IR MEASUREMENTS OF CROSS SECTIONS OF COLD C3 H8 IN THE 7 - 15 µm FOR TITAN
15 min 4:21
KEEYOON SUNG, GEOFFREY C. TOON, LINDA R. BROWN, Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Dr.,Pasadena, CA 91109; ARLAN W. MANTZ, Dept. of Physics,
Connecticut College, New London, CT 06320; MARY ANN H. SMITH, Science Directorate, NASA Langley
Research Center, Hampton, VA 23681.
To support atmospheric remote sensing of Titan, the absorption cross sections of N2 -broadened C3 H8 were obtained at
temperatures between 145 and 296 K. For this, 35 spectra of pure- and N2 -broadened propane were recorded in the 670
to 1900 cm-1 region using a Fourier transform spectrometer (Bruker IFS-125HR) at the Jet Propulsion Laboratory. A
20.38 cm path temperature-stabilized cryogenic absorption cell was used, which was developed at Connecticut College
and described previously [1]. We report the absorption cross sections at the various cold temperatures for nine strong fundamental bands (ν26 , ν8 , ν21 , ν20 , ν7 , ν19 , ν18 , ν4 , ν24 ) as well as for many contributions from hot and combination bands.
In addition, we present results from ’pseudo -line generation’ (http://mark4sun.jpl.nasa.gov/data/spec/Pseudo/Readme),
which includes mean intensities and effective lower state energies on a 0.005 cm−1 frequency grid determined in the 690
- 1536 cm−1 region from all 35 high-resolution laboratory spectra. It was observed that the pseudo lines reproduce all
the observed spectral transmittances well within 3% and the C3 H8 amounts within 4% on the average. The measured
cross sections and synthetic spectra from the pseudoline compilation are compared to earlier work, including the C3 H8 +N2
spectra recorded at PNNL [2] and line-by-line predictions available [3, 4].a b
a [1] K. Sung, A. W. Mantz, M. A. H. Smith, et al., J Mol Spectrosc 262, 122, 2010.; [2] S. W. Sharpe, et al., Appl Spectrosc 58, 1452, 2004.; [3] J.
M. Flaud et al., Mol Phys 108, 699, 2010.; [4] J. M. Flaud et al., J Chem Phys 114, 9361, 2001.
b The research described in this paper was performed at the Jet Propulsion Laboratory, California Institute of Technology and at The College of William
and Mary under contracts with National Aeronautics and Space Administration. US Government Support Acknowledged.
MJ11
15 min 4:38
QUANTITATIVE MEASUREMENT OF INTEGRATED BAND INTENSITIES OF ISOPRENE AND FORMALDEHYDE
The OH-initiated oxidation of isoprene, which is one of the primary volatile organic compounds produced by vegetation,
is a major source of atmospheric formaldehyde and other oxygenated organics. Both molecules are also known products
of biomass burning. Absorption coefficients and integrated band intensities for isoprene and formaldehyde are reported in
the 600 -– 6500 cm−1 region. The pressure broadened (1 atmosphere N2 ) spectra were recorded at 278, 298 and 323 K
in a 19.96 cm path length cell at 0.112 cm−1 resolution, using a Bruker 66V FTIR. Composite spectra are composed of a
minimum of seven pressures at each temperature for both molecules. These data are part of the PNNL Spectral Database,a
which contains quantitative spectra of over 600 molecules. These quantitative spectra facilitate atmospheric monitoring for
both remote and in situ sensing and such applications will be discussed.
a Timothy
J. Johnson, Luisa T. M. Profeta, Robert L. Sams, David W. T. Griffith, Robert L. Yokelson Vibrational Spectroscopy 53(1);97-102 (2010).
141
MJ12
15 min 4:55
QUANTITATIVE INTENSITY STUDIES OF THREE GAS-PHASE MONOTERPENES IN THE INFRARED: αPINENE, β-PINENE AND D-LIMONENE
Monoterpenes are a class of biogenic volatile organic compounds (VOCs) whose general formula is C10 H16 . Like other
VOCs, monoterpenes play an important role in the atmosphere as they are produced by vegetation in large quantities,
and have recently been discovered in biomass burning plumes. Absorption coefficients and integrated band intensities
are reported in the 600 -– 6500 cm−1 region for three monoterpenes: α-pinene, β-pinene and d-limonene. The pressure
broadened (1 atmosphere N2 ) spectra were recorded in a 19.96 cm path length cell with 0.112 cm−1 resolution at two
temperatures and a minimum of six different partial pressures using a Bruker 66V FTIR. These data are part of the PNNL
Spectral Database,a which contains quantitative spectra of over 600 molecules. Potential atmospheric applications will be
discussed
a Timothy
J. Johnson, Luisa T. M. Profeta, Robert L. Sams, David W. T. Griffith, Robert L. Yokelson Vibrational Spectroscopy 53(1);97-102 (2010).
MJ13
10 min 5:12
COMPARISON OF EXPERIMENTAL AND THEORETICAL ABSORPTION CROSS SECTIONS OF PFBAm
PAUL J. GODIN, STEPHANIE CONWAY, Department of Physics, University of Toronto, 60 St. George St.,
Toronto, ON, M5S 1A7, Canada; ANGELA HONG, Department of Chemistry, University of Toronto, 80
St. George St., Toronto, ON, M5S 3H6, Canada; KARINE LE BRIS, Department of Physics, St. Francis
Xavier University, Antigonish, Nova Scotia, B2G 2W5, Canada; SCOTT MABURY, Department of Chemistry, University of Toronto, 80 St. George St., Toronto, ON, M5S 3H6, Canada; and KIMBERLY STRONG,
Department of Physics, University of Toronto, 60 St. George St., Toronto, ON, M5S 1A7, Canada.
We present a comparison of theoretical and experimental absorption cross sections of perfluorotributylamine (PFBAm).
PFBAm is a fully-fluorinated liquid commonly used in electronic reliability and quality testing. PFBAm vapours can be
considered potential greenhouse gases due being radiatively active in the mid-IR spectral region and having a long atmospheric lifetime.
Theoretical density functional theory (DFT) calculations are done using the B3LYP method and the 6-311G(d,p) basis
set. The calculations have determined the optimized geometrical configuration and IR intensities and wavenumbers of the
harmonic frequencies for both PFBAm (N(CF2CF2CF2CF3)3) and its congener (F3CN(CF2CF2CF2CF3)2).
Experimental cross sections are derived from Fourier transform spectroscopy performed from 600-1450 cm−1 at a resolution of 0.02 cm−1 for a temperature range of 273-296 K. These experimental results are compared to our theoretical
calculations and both are compared to previous measurements of PFBAm made at room temperature by Young et al.
142
MJ14
15 min 5:24
INVESTIGATING ATMOSPHERIC OXIDATION WITH MOLECULAR DYNAMICS IMAGING AND SPECTROSCOPY
W. G. MERRILL, A. S. CASE, and F. N. KEUTSCH, Department of Chemistry, University of Wisconsin,
Madison, WI 53706.
Volatile organic compounds (VOCs) in the Earth’s atmosphere constitute trace gas species emitted primarily from the biosphere, and are the subject of inquiry for a variety of air quality and climate studies. Reactions intiated (primarily) by
the hydroxyl radical (OH) lead to a myriad of oxygenated species (OVOCs), which in turn are prone to further oxidation. Investigations of the role that VOC oxidation plays in tropospheric chemistry have brought to light two troubling
scenarios: (1) VOCs are responsible in part for the production of two EPA-regulated pollutants—tropospheric ozone and
organic aerosol—and (2) the mechanistic details of VOC oxidation remain convoluted and poorly understood. The latter
issue hampers the implementation of near-explicit atmospheric simulations, and large discrepancies in OH reactivity exist
between measurements and models at present. Such discrepancies underscore the need for a more thorough description of
VOC oxidation.
Time-of-flight measurements and ion-imaging techniques are viable options for resolving some of the mechanistic and energetic details of VOC oxidation. Molecular beam studies have the advantage of foregoing unwanted bimolecular reactions,
allowing for the characterization of specific processes which must typically compete with the complex manifold of VOC
oxidation pathways. The focus of this work is on the unimolecular channels of organic peroxy radical intermediates, which
are necessarily generated during VOC oxidation. Such intermediates may isomerize and decompose into distinct chemical
channels, enabling the unambiguous detection of each pathway. For instance, a (1 + 1′ ) resonance enhanced multiphoton
ionization (REMPI) scheme may be employed to detect carbon monoxide generated from a particular unimolecular process. A number of more subtle mechanistic details may be explored as well. By varying the mean free path of the peroxy
radicals in a flow tube, the role of collisional quenching in these unimolecular channels can be assessed. Reactive species
may also be introduced to explore the competition between bimolecular and unimolecular pathways. Vibrational modes
may also be excited by an IR laser, providing insight about the role of vibrational mediation in VOC oxidation.
MJ15
10 min 5:41
PHOTODISSOCIATION DYNAMICS OF 2-BROMOETHYLNITRITE AT 351 NM AND C-C BOND FISSION IN THE
β-BROMOETHOXY RADICAL PRODUCT
LEI WANG, Department of Chemistry, The University of Chicago, Chicago, IL 60637; RABI CHHANTYALPUN, Department of Chemistry, The Ohio State University, Columbus, OH 43210; MATT D. BRYNTESON,
Department of Chemistry, The University of Chicago, Chicago, IL 60637; TERRY A. MILLER, Department
of Chemistry, The Ohio State University, Columbus, OH 43210; and LAURIE J. BUTLER, Department of
Chemistry, The University of Chicago, Chicago, IL 60637.
We used a crossed laser-molecular beam scattering experiment to investigate the primary photodissociation channels of
bromoethylnitrite at 351 nm. Only the O-NO bond fission channel forming the β-bromoethoxy radical and NO, no HBr
photoelimination, was detected upon 351 nm photoexcitation,. The subsequent decomposition of the highly vibrational
excited β-bromoethoxy radical to formaldehyde + CH2 Br was also investigated.
143
MJ16
PHOTOCHEMISTRY OF ACETONE IN SIMULATED ATMOSPHERE
15 min 5:53
T. CHAKRABORTY, A. K. GHOSH and A. CHATTOPADHYAY, Department of Physical Chemistry, Indian
Association for the cultivation of science, Calcutta 700032, India. E-mail: [email protected].
Acetone has been identified to be one of the dominant non-methane organic species present in our atmosphere with an
annual budget of ∼ 40 − 60 T g (1012 g). It has been proposed that the major fraction of atmospheric acetone (∼ 65%)
is removed via photodissociation channel. Numerous laboratory investigations were devoted in the past to understand
how the reactions are evolved in presence of oxygen and water vapour. Our recent study, wherein the photo products are
probed using a tandem methodology of quadrupole mass spectrometry and gas-phase infrared spectroscopy reveals that
a significant fraction of acetone is converted to formic acid in presence of oxygen when exposed to ultraviolet light of
wavelengths available in troposphere. The measurement has been repeated with other linear and cyclic ketones and some
of their deuterated analogues. The details of our findings will be presented in the talk.
144
MK. INFRARED/RAMAN
MONDAY, JUNE 17, 2013 – 1:30 PM
Chair: JENNIFER VAN WIJNGAARDEN, University of Manitoba, Winnipeg MB, Canada
MK01
15 min 1:30
ROTATIONALLY-RESOLVED SPECTROSCOPY OF THE BENDING MODES OF DEUTERATED WATER DIMER
JACOB T. STEWART, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL
61801; BENJAMIN J. McCALL, Departments of Chemistry and Astronomy, University of Illinois at UrbanaChampaign, Urbana, IL 61801.
High-resolution spectroscopy of small gas-phase water clusters has provided a wealth of information regarding the intermolecular interactions between water molecules. Water dimer is of particular interest because high-resolution spectroscopy
can yield detailed information about the water pair potential. While there have been extensive studies of water dimer
throughout the microwave and infrared regions of the spectrum, to date there has been no reported high-resolution spectrum of the intramolecular bending modes of water dimer. We have obtained rotationally-resolved spectra of the bending
modes of deuterated water dimer (D2 O)2 , which are, to our knowledge, the first reported spectra of the bending modes of
water dimer with rotational resolution. Dimers were produced in a supersonic expansion by bubbling Ar or He through
D2 O and expanding the mixture through a 150 µm × 12 mm slit. The expansion was then probed using continuous wave
cavity ringdown spectroscopy with light generated by a quantum cascade laser (QCL) operating near 8.5 µm. We have
assigned the Ka = 1 ← 0 and Ka = 2 ← 1 sub-bands of the bending mode belonging to the hydrogen bond donor and
have observed additional transitions which we attribute to the bending mode associated with the hydrogen bond acceptor.
MK02
15 min 1:47
INFRARED SPECTROSCOPY OF ((CH3 )3 N)n -H -H2 O (n=1-3): STRUCTURES AND DISSOCIATION CHANNELS
OF PROTONATED MIXED CLUSTERS AROUND A MAGIC NUMBER
+
University, Sendai 980-8578, Japan; JER-LAI KUO, Institute of Atomic and Molecular Science, Academia
The magic number behavior of ((CH3 )3 N)n -H+ -H2 O clusters at n = 3 is investigated by applying infrared spectroscopy to
the clusters of n = 1-3. a Structures of these clusters are determined in conjunction with density functional theory calculations. Dissociation channels upon infrared excitation are also measured, and their correlation with the cluster structures
is examined. It is demonstrated that the magic number cluster has a closed-shell structure, in which the water moiety is
surrounded by three (CH3 )3 N molecules. Large rearrangement of the cluster structures of n = 2 and 3 before dissociation,
which has been suggested in the mass spectrometric study, b is confirmed on the basis of the structure determination by
infrared spectroscopy.
a R.
b S.
Shishido, J. -L. Kuo and A. Fujii J. Phys. Chem. A 116, 6740, 2012.
Wei, W. B. Tzeng, R. G. Keesee and A. W. Castleman, Jr. J. Am. Chem. Soc. 113, 1960, 1991.
145
MK03
15 min 2:04
MAPPING CONFORMATIONAL ENERGY BARRIERS IN HYDRATED RUBIDIUM ION CLUSTERS
HAOCHEN KE, AMY L. NICELY, JAMES M. LISY, Department of Chemistry, University of Illinois at
Urbana-Champaign, Urbana, IL 61801.
In gas-phase hydrated metal ion cluster systems, the stability of a particular conformer is determined intrinsically by the
internal competition between ion—water electrostatic interactions and water—water hydrogen bonding interactions. The
balance between these interactions depends largely upon the internal energy, or temperature, of the cluster ion, which is
determined by the evaporation pathway. At the temperature associated with cluster ions formed via evaporation of argon,
i. e. ≈ 100 K, the global minimum-energy conformer is generally expected. However, if the kinetic energy of the cluster is
adequately low, conformers with higher potential energy might not have sufficient energy to overcome energetic barriers,
i. e. breaking pre-existing hydrogen bonds, to rearrange into a lower or global minimum-energy conformer. Therefore,
kinetically trapped, high potential energy conformers could coexist with the global minimum-energy conformer in the
cluster ensemble. Rb+ (H2 O)m Ar (m = 3 − 5) clusters were studied systematically to map the potential energy barriers
of the hydrated rubidium cluster systems. Infrared photodissociation spectra monitoring both [Ar] and [Ar+H2 O] loss
channels aided by parallel ab initio, RRKM-EE and thermodynamics calculations provided definitive evidence to the
existence of conformational energy barriers.
MK04
15 min 2:21
IR SPECTROSCOPY OF [Ag·(CO2 )n ] CLUSTERS: IMPLICATIONS FOR REDUCTIVE ACTIVATION OF CO2
−
BENJAMIN J. KNURR and J. MATHIAS WEBER, JILA and Department of Chemistry and Biochemistry,
University of Colorado, Boulder, CO 80309.
Reduction of CO2 is an essential step in its chemical conversion from a greenhouse gas to useable fuel stocks, but is
energetically unfavorable. Association with anions has been shown to facilitate partial charge transfer to a target CO2
molecule, which could be a significant step towards CO2 recycling. However there is still much uncertainty in the role
of solvent effects on these chemical processes. We present infrared spectra of [Ag·(CO2 )n ]− (n = 2 − 11) to elucidate
the nature of the charge carrier in the cluster, the effects of solvation on the charge distribution and the amount of
reductive activation of CO2 in the presence of a Ag anion. The structures of the [Ag·(CO2 )n ]− clusters are discussed in
the framework of density functional theory. We compare and contrast the findings of [Ag·(CO2 )n ]− to those recently
published on [Au·(CO2 )n ]− [1].
1. B.J. Knurr and J.M. Weber, J. Amer. Chem. Soc., 134 (2012) 18804-18808.
MK05
HIGH-RESOLUTION INFRARED SPECTROSCOPY OF Ge2 C3
15 min 2:38
S. THORWIRTH, V. LUTTER, S. SCHLEMMER, I. Physikalisches Institut, Universität zu Köln, 50937 Köln,
Germany; T. F. GIESEN, Universität Kassel, Fachbereich 10 - Physik, 34132 Kassel, Germany; J. GAUSS,
Institut für Physikalische Chemie, Universität Mainz, 55099 Mainz, Germany.
Carbon-rich systems are of great importance in diverse areas of research like material science as well as astro- and structural
chemistry. Despite this relevance, our knowledge of smaller cluster units is still fragmentary, particularly with respect to
investigations at high-spectral resolution in the gas phase. Unequivocal assignment of spectral features to their molecular
carriers is critically dependent on predictions from high-level quantum-chemical calculations. In turn, high-resolution
studies provide useful information to assess the predictive power of quantum-chemical methods. This is particularly
interesting for cluster systems harboring heavy elements for which so far relatively little is known from experiment. With
this contribution, we would like to present a recent gas-phase study of a polyatomic germanium-carbon cluster, linear
Ge2 C3 (Ge=C=C=C=Ge), which was previously studied in an Ar matrixa . The cluster was produced through laser ablation
of germanium-graphite sample rods and observed in a free jet at wavelengths around 5µm. Additionally, quantum-chemical
calculations of Ge2 C3 were performed at the CCSD(T) level of theory. The production and observation of Ge2 C3 suggests
that many more binary clusters should be amenable to high-resolution spectroscopic techniques not only in the infrared but
also in the microwave region.
a D.
L. Robbins, C. M. L. Rittby, and W. R. M. Graham, J. Chem. Phys. 114, 3570 (2001).
146
MK06
FIRST OBSERVATION OF CO TRIMER AND A NEW LOOK AT CO DIMER
15 min 2:55
University of Calgary, 2500 University Dr., N.W., Calgary, AB T2N 1N4, Canada; K.H. MICHAELIAN,
Natural Resources Canada, CanmetENERGY, 1 Oil Patch Drive, Suite A202, Devon, AB T9G 1A8, Canada;
A.R.W. McKELLAR, National Research Council of Canada, Ottawa, ON K1A 0R6, Canada.
A broad-band (2135 to 2200 cm−1 ) infrared spectrum is recorded using a tunable quantum cascade laser to probe a
supersonic jet expansion of a dilute mixture of carbon monoxide in helium, giving an effective rotational temperature of
about 2.5 K. Structure in the region of 2144 cm−1 is assigned to the previously elusive CO trimer.a In spite of interference
from the CO dimer and some remaining unexplained details, there is strong evidence for a planar, cyclic, C-bonded trimer
structure, with C3h symmetry and 4.42 Å intermolecular separation, in agreement with theoretical calculations.b A modest
vibrational blue-shift of +0.85 cm−1 is observed for the trimer, as compared to +0.71 cm−1 for the C-bonded form of the
dimer (and −1.28 cm−1 for the O-bonded form).
Analysis of the new dimer spectrum reveals the first known excited state (vCO = 1) levels with A+ symmetry, and establishes that resonant vibrational splittings are small (<0.2 cm−1 ) for both the C-bonded and O-bonded dimer isomers. The
dimer spectrum extends over a surprisingly large range, with somewhat reduced intensity above 2150 cm−1 . A total of 28
new rotational level stacks having A− symmetry are assigned for vCO = 1 on the basis of combination differences, adding
to the 8 stacks previously known,c and extending up to 51 cm−1 above the vCO = 1 origin. For the first 13 stacks we
can establish a correspondence between vCO = 0 and 1, and give labels in terms of values for K, for the low frequency
intermolecular geared-bend mode, and for the intramolecular mode (in phase or out of phase C−O stretch).
a M.
Rezaei et al., J. Chem. Phys. 138, 071102 (2013).
Vissers et al., J. Chem. Phys. 122, 054306 (2005); T.A. Ford, Spectrochim. Acta A 64, 1151 (2006).
c M.D. Brookes and A.R.W. McKellar, J. Chem. Phys. 111, 7321 (1999); K.A. Walker et al., J. Chem. Phys. 113, 6618 (2000).
b G.W.M.
MK07
15 min 3:12
OBSERVATION OF COMBINATION BANDS INVOLVING INTERMOLECULAR VIBRATIONS OF N2 O-N2 , N2 OOCS AND N2 O-CO2 COMPLEXES USING AN EXTERNAL CAVITY QUANTUM CASCADE LASER
University of Calgary, 2500 University Dr., N.W., Calgary, Alberta T2N 1N4, Canada; A.R.W. McKELLAR,
Spectra of the weakly-bound N2 O-CO2 , N2 O-OCS, and N2 O-N2 complexes in the region of the N2 O ν1 fundamental band
(∼2224 cm−1 ) are observed in a pulsed supersonic slit jet expansion probed with a quantum cascade laser. One new band is
observed for each complex: two combination bands involving the intermolecular in-plane bending for N2 O-CO2 and N2 ON2 complexes, and the out-of-plane torsional vibration for N2 O-OCS. The resulting intermolecular frequencies are 34.17,a
17.11 and 22.33 cm−1 for N2 O-CO2 , N2 O-OCS, and N2 O-N2 complexes, respectively. The intermolecular vibrations
provide clear spectroscopic data against which theory can be benchmarked. These results will be discussed, along with
a brief introduction to our pulsed-jet supersonic apparatus which has been retrofitted by an infrared cw external-cavity
quantum cascade laser (QCL) manufactured by Daylight Solutions. The QCL is used in the rapid-scan signal averaging
mode. Although the repetition rate of the QCL is limited by its PZT scan rate, which is 100 Hz, we describe a simple
technique to increase the effective repetition rate to 625 Hz. In addition, we have significantly reduced the long term
frequency drift of the QCL by locking the laser frequency to the sides of a reference line.
a Limin
Zheng, Soo-Ying Lee, Yunpeng Lu, and Minghui Yang, J. Chem. Phys. 138, 044302 (2013).
147
MK08
INFRARED SPECTRA OF THE NE2 -N2 O, AR2 -N2 O TRIMERS
15 min 3:29
M. REZAEI, N. MOAZZEN-AHMADI, Department of Physics and Astronomy, University of Calgary, 2500
University Dr., N.W., Calgary, Alberta T2N 1N4, Canada; K.H. MICHAELIAN, Natural Resources Canada,
CanmetENERGY, 1 Oil Patch Drive, Suite A202 Devon, Alberta, T9G 1A8, Canada; A.R.W. McKELLAR,
Spectra of the van der Waals trimers Ar2 -N2 O and Ne2 -N2 O are studied in the region of the N2 O ν1 fundamental
(∼2224 cm−1 ) using a tunable quantum cascade laser to probe a pulsed supersonic expansion from a slit jet nozzle. Improved data are also obtained for the dimers Ar-N2 O and Ne-N2 O, with the latter representing a significant improvement
on the best previous results. As well, a feature in the spectrum is tentatively assigned as the Q-branch of Ar3 -N2 O. The
observed vibrational shifts for Nen -N2 O are almost exactly linear for n = 0-2. However, for Arn -N2 O the n = 2 band origin
is slightly blue-shifted compared to the linear prediction, and the n = 3 origin (if correct) is more significantly blue-shifted
(by 0.09 cm−1 ).
Intermission
MK09
15 min 4:00
INFRARED SPECTRUM OF THE (CO2 )2 -N2 O TRIMER MEASURED IN N2 O ν1 AND ν3 REGIONS.
J. NOROOZ OLIAEE, N. MOAZZEN-AHMADI, Department of Physics and Astronomy, University of Calgary, 2500 University Dr., N.W., Calgary, Alberta T2N 1N4, Canada; A.R.W. McKELLAR, National Research
Council of Canada, Ottawa, Ontario, K1A 0R6, Canada.
Infrared spectra of the (CO2 )2 -N2 O trimer are observed by exciting the ν1 and ν3 fundamental stretching vibrations of
the N2 O moiety (around 1285 cm−1 and 2224 cm−1 respectively). Spectra are recorded using a pulsed supersonic jet
apparatus with a tunable diode laser probe. Ground state parameters were previously determined from a microwave study.a
Analysis of the infrared spectra reveals information on the vibrational shifts upon complex formation as well as molecular
parameters for the excited states. Our cluster calculation program yields a minimum energy structure very similar to that
from the Orient programa but in slightly better agreement with the experimental structure. Our cluster calculations indicate
a close resemblance of the two lowest energy isomers to those of (CO2 )2 -OCS.
a R.
A. Peebles, S. A. Peebles, and R. L. Kuczkowski Mol. Phys. 96, 1355 (1999).
MK10
OBSERVATION OF A PLANAR ISOMER OF THE N2 O-(C2 H2 )2 TRIMER
15 min 4:17
S. SHEYBANI-DELOUI, J. NOROOZ OLIAEE, M. REZAEI, N. MOAZZEN-AHMADI, Department of
Physics and Astronomy, University of Calgary, 2500 University Drive North West, Calgary, Alberta, Canada
T2N 1N4; A.R.W. McKELLAR, National Research Council of Canada, Ottawa, Ontario, Canada K1A 0R6.
Infrared spectra of a planar isomer of the N2 O-(C2 H2 )2 are observed in the region of ν1 fundamental band of N2 O monomer
(∼2224 cm−1 ) using a quantum cascade laser to probe a pulsed supersonic slit jet expansion. The band is simulated by
an asymmetric top Hamiltonian with rotational constants of A = 2871 MHz, B = 1140 MHz, C = 816 MHz and hybrid
a/b-type transitions. It shows a relatively large blue-shift of about 9 cm−1 with respect to the N2 O monomer band origin. In
addition to the normal istopologue, 15 N2 O-(C2 H2 )2 and N2 O-(C2 D2 )2 are also observed. Here, we present our observation
and experimental results which agree fairly well with a semi-empirical calculation which indicates that the lowest energy
isomer has a planar structure very similar to that of OCS-(C2 H2 )2 .a
a J.
Norooz Oliaee, A.R.W. McKellar, and N. Moazzen-Ahmadi, Chem. Phys. Lett. 512, 167 (2011).
148
MK11
15 min 4:34
INFRARED SPECTRUM OF THE CS2 TETRAMER: OBSERVATION OF A STRUCTURE WITH D2d SYMMETRY
M. REZAEI, J. NOROOZ OLIAEE, N. MOAZZEN-AHMADI, Department of Physics and Astronomy, University of Calgary, 2500 University Dr., N.W., Calgary, Alberta T2N 1N4, Canada; A.R.W. McKELLAR,
Infrared spectra of carbon disulphide clusters are studied in the region of the CS2 ν3 fundamental band (∼1535 cm−1 ),
using a tuneable diode laser to probe a pulsed supersonic slit jet expansion. A symmetric rotor parallel band at 1551.438
cm−1 is assigned to CS2 tetramer. The likely structure is a staggered and tilted barrel with D2d symmetry, similar to
the previously observed oblate tetramer of nitrous oxide, in reasonable agreement with that calculated from an empirical
CS2 intermolecular potential function. This is the first high-resolution spectroscopic detection of CS2 tetramer, and the
calculations suggest that there could be other lower energy isomers of (CS2 )4 which are not yet observed.
MK12
15 min 4:51
INFRARED SPECTROSCOPIC STUDY ON FERMI RESONANCE OF THE EXCESS PROTON VIBRATION IN BINARY CLUSTERS
University, Sendai 980-8578, Japan; JER-LAI KUO, Institute of Atomic and Molecular Sciences Academia
Infrared photodissociation spectroscopy was applied to (CH3 )3 N-H+ -X (X = Ar, N2 , CO, C2 H2 , H2 O, CH3 OH, C2 H5 OH,
CH3 COCH3 , NH3 , CH3 NH2 , (CH3 )3 N) clusters, and the excess proton vibration (N-H+ stretching vibration) was observed. In a protonated binary cluster, the excess proton location and its magnitude of delocalization is determined by the
difference of the proton affinities of the two componentsa. We observed that the N-H+ stretching frequency goes down as
the proton affinity of X increases. When the N-H+ stretching frequency gets to the overtone region of the N-H+ bending
mode, complicated Fermi resonance was always seen. This indicates that the Fermi resonance necessarily occurs in the
excess proton vibration at this frequency region. At least two vibrations seem to couple with the N-H+ stretching mode,
demonstrating the requirement of multi-dimensional mode analyses to understand this coupling. In addition, we confirmed
that the Fermi resonance also occurs by changing the proton affinity of the amine moiety (from (CH3 )3 N to CH3 NH2 and
(CH3 )2 NH).
a J.
R. Roscioli, L. R. McCunn, M. A. Johnson, Science 316, 249 (2007).
MK13
15 min 5:08
THEORETICAL STUDY ON FERMI RESONANCE OF THE EXCESS PROTON VIBRATION IN BINARY CLUSTERS
JER-LAI KUO, JAKE TAN, Institute of Atomic and Molecular Sciences Academia Sinica, Taipei 10617, Taiwan; RYUNOSUKE SHISHIDO, ASUKA FUJII, Department of Chemistry, Graduate School of Science,
Tohoku University, Sendai 980-8578, Japan.
In protonated binary clusters, location and magnitude of delocalization of the excess proton is shown to correlate to the
difference of the proton affinities of the two componentsa. Theoretical calculations on a series of protonated binary clusters
have shown that Fermi resonance can occur in clusters containing amines. For examples, in (CH3 )3 N-H+ -X, the N-H+
stretching frequency is high than the first overtone of N-H+ bending modes. As the N-H+ stretching frequency decreases
by increasing the proton affinity of X, Fermi resonance inevitably shall occur. At least both N-H+ bending modes seem to
couple with the N-H+ stretching mode; we performed multi-dimensional mode analyses to understand this coupling.
a J.
R. Roscioli, L. R. McCunn, M. A. Johnson Science316, 249 (2007).
149
MK14
10 min 5:25
MUTUAL CO-ASSIGNMENT OF THE CALCULATED VIBRATIONAL FREQUENCIES IN THE GROUND AND
LOWEST EXCITED ELECTRONIC STATES
YURII N. PANCHENKO, Laboratory of Molecular Spectroscopy, Division of Physical Chemistry, Department of Chemistry, Lomonosov Moscow State University, Moscow 119991, Russian Federation..
The shifts of the molecular vibrational frequencies when going from the ground electronic state to the lowest excited
electronic states pose some problems for the mutual co-assignment of the calculated vibrational frequencies in the different
excited states. The trans-C2 O2 F2 shift of the frequency of the symmetrical ν(C=O) stretching vibration between the S0
and T1 is 373 cm−1 .
The feasibility of mutual co-assignments of the vibrational frequencies in these electronic states has been demonstrated for
trans-C2 O2 F2 . Matrices analogous to the Duschinsky matrixa were used to juxtapose the ag vibrational frequencies of this
molecule calculated at the CASPT2/cc-pVTZ level in the ground S0 and excited triplet T1 and singlet S1 electronic states.
The analog of the Duschinsky matrix D was obtained for this molecule using the equation D = (LI )−1 LII where LI
and LII are the matrices of the vibrational modes (normalized atomic displacements) obtained by solving the vibrational
problems for the S0 and T1 electronic states, respectively. Choosing the dominant elements in columns of the D matrix and
permuting these columns to arrange these elements along the diagonal of the transformed matrix D∗ makes it possible to
establish the correct mutual co-assignments of the calculated ag vibrational frequencies of the trans-C2 O2 F2 molecule in
the S0 and T1 electronic states. The analogous procedure was performed for the trans-C2 O2 F2 molecule in the T1 and S1
excited electronic states. The recent reassignments of the ν2 and ν3 calculated vibrational frequencies in the trans-C2 O2 F2
molecule in the ground state were also obtained for the triplet T1 and singlet S1 excited electronic states.
The approach set forth in this text makes it possible to juxtapose the calculated vibrational frequencies of the same molecule
in the different electronic states and to refine the assignments of these frequencies. This is essential in correctly analyzing
the vibronic spectra of a molecule under investigation.
a F.
Duschinsky, Acta Physicochim. URSS, 7 (4), 551–566 (1937).
150
TA. MINI-SYMPOSIUM: SPECTROSCOPY TESTS OF FUNDAMENTAL
PHYSICS
Chair: ANATOLY TITOV, St. Petersburg Nuclear Physics Institute, Gatchina, Russia
TA01
INVITED TALK
30 min 8:30
TOWARDS THE FIRST MEASUREMENT OF PARITY VIOLATION IN CHIRAL MOLECULES EW ATTEMPTS
AND FUTURE PROSPECTIVE
PETER SCHWERDTFEGER, Centre for Theoretical Chemistry and Physics, The New Zealand Institute for
Advanced Study, Massey University Auckland, Auckland, New Zealand.
Parity violation (PV) effects in atomic transitions have been measured and calculated to high accuracy confirming the socalled standard model in particle physics. The Z-boson exchange between electrons and nucleons leads to a small energy
difference between enantiomers of chiral molecules. There is, however, no experimental verification yet of this distinct
symmetry breaking effect despite many attempts. Current high-resolution optical spectroscopy experiments carried out
in the CO2 laser frequency range (878-1108 cm-1) in Christian Chardonnet group in Paris achieve resolutions below 1
Hz. Recent calculations in our group applying the standard model show that PV effects in vibrational transitions of chiral
methane derivates CFXYZ (X,Y,Z= H, Cl, Br, I) are in the mHz range and below the detection limit. Our research group is
therefore searching for better molecules including heavy elements (because of the PV Z 5 scaling with nuclear charge Z) to
achieve enhanced PV splittings in the Hz range. New promising candidates are presented in collaboration with the French
PV initiative, which aims at a 100 mHz resolution in Ramsay-Fringes experiments using quantum cascade lasers. Another
future alternative is single-molecule spectroscopy in traps at ultra-cold temperatures.
TA02
15 min 9:05
RIGOROUS RELATIVISTIC METHODS FOR ADDRESSING P- AND T -NONCONSERVATION IN HEAVYELEMENT MOLECULES
TIMO FLEIG, Laboratoire de Chimie et Physique Quantiques, Université Paul Sabatier Toulouse 3, Toulouse,
France.
A new and rigorous method for accurate ab-initio calculations of the electron electric dipole moment P, T -odd interaction
constant is presented. The approach uses string-based Configuration Interaction wavefunctionsa and Dirac four-component
spinors as one-particle basis functions, and the P, T -odd constant is obtained as an expectation value over these correlated
wavefunctions. The method has been applied to the HfF+ molecular ion to determine spectroscopic constants for four
low-lying electronic states. For one of these states (Ω = 1) we have determined a new accurate benchmark valueb for
the effective electric field Eeff correlating 34 valence and outer atomic core electrons and using wavefunction expansions
with nearly 5 · 108 coefficients. For the Ω = 1 state of the ThO molecule the first ab-initio result for the electron EDM
interaction constant is presented.
Aspects of modern all-electron relativistic many-body approaches applicable to both atoms and molecules will be discussed, including perspectives for the treatment of other interesting candidate systems and P- or P, T -non-conserving
effects in molecular systems.
a S.
Knecht, H. J. Å. Jensen and T. Fleig J. Chem. Phys. 132, 014108 (2010)
T. Fleig, H. J. Å. Jensen, J. Olsen and L. Visscher J. Chem. Phys. 124, 104106 (2006)
Fleig and M. K. Nayak Phys. Rev. X XXX, XXXX (submitted).
b T.
151
TA03
15 min 9:22
PARITY VIOLATION IN CHIRAL MOLECULES: CURRENT STATUS OF THEORY AND SPECTROSCOPIC EXPERIMENT
MARTIN QUACK, GEORG SEYFANG, Physical Chemistry, ETH Zurich, CH-8093 Zurich, Switzerland.
In the ordinary quantum chemistry based on the electromagnetic interaction the ground state energies of enantiomers of
chiral molecules are exactly the same by symmetry. Parity violation in electroweak interactions leads to a small “parity
violating” energy difference ∆pv E between the ground states of enantiomers corresponding to a heat of reaction for
−11
stereomutation ∆R H⊖
J mol−1 , (typically, or about 100 aeV corresponding to about 10−12 cm−1 ). After our
0 ≃ 10
finding (in 1995) that a revised theory leads to about a factor of 10 to 100 higher values than previously calculated in
older theoretical work prior to 1995, the theoretical results from many groups have now essentially converged to the new
values (see reviews a b c ). However, experimental results for ∆pv E are still missing. We shall discuss the status of ongoing
experiments in the Zürich group to detect this exceedingly small effect by spectroscopy following a scheme proposed in
1986 d e and shall discuss also the comparison with other efforts.
a M.
Quack, Frontiers in Spectroscopy, in Faraday Discussions, Vol. 150, pp. 533-565, 2011.
Quack, Fundamental Symmetries and Symmetry Violations from High Resolution Spectroscopy, in Handbook of High Resolution Spectroscopy,
Vol. 1, Chapt. 18, pp. 659-722 (Eds.: M. Quack, F. Merkt), Wiley, Chichester, New York, 2011, ISBN 978-0-470-06653-9.
c M. Quack, J. Stohner, M. Willeke, High-resolution spectroscopic studies and theory of parity violation in chiral molecules, Annu. Rev. Phys. Chem.,
2008, 59, 741-769.
d M. Quack, On the measurement of the parity violating energy difference between enantiomers, Chem. Phys. Lett., 1986, 132, 147-153.
e P. Dietiker, M. Quack, A. Schneider, G. Seyfang, F. Ünlü, IR-laser induced population transfer from highly populated rotational levels of NH in
3
a molecular beam, in Proceedings of the 18th Symposium on Atomic, Cluster and Surface Physics 2012 (SASP 2012), Alpe d‘Huez, France, 22 to 27
January 2012, pp. 263-267 (Eds.: M. Lewerenz, O. Dutuit, R. Marquardt), Innsbruck University Press (IUP), Innsbruck, 2012, ISBN 978-3-902811-42-4;
and to be published.
b M.
TA04
15 min 9:39
A COMBINED SYNCHROTRON-BASED HIGH RESOLUTION FTIR AND DIODE LASER JET INFRARED SPECTROSCOPY STUDY OF THE CHIRAL MOLECULE CDBrClF
S. ALBERT, K. KEPPLER ALBERT, M. QUACK, PHYSICAL CHEMISTRY, ETH ZÜRICH, CH-8093
ZÜRICH, SWITZERLAND; PH. LERCH, SWISS LIGHT SOURCE, PAUL-SCHERRER-INSTITUTE, CH-5232
VILLIGEN, SWITZERLAND ; V. BOUDON, LABORATOIRE CARNOT DE BOURGOGNE, UNIVERSITE DE
BOURGOGNE, F-21078 DIJON, FRANCE.
The experimental detection of molecular parity violationa ∆P V E is of great interest because of its importance in the
understanding of fundamental aspects of molecular dynamics and symmetries. One possible method for this is measuring
rovibrational or rotational frequency shifts in the infrared or microwave spectra of enantiomersb. For that reason we
have measured and analysed the rotationally resolved infrared spectrum of CDBrClF as a prototype spectrum for a chiral
molecule using three different techniques. The spectrum has been recorded at room temperature with the Zurich Bruker
IFS spectrometer ZP 2001c and with the Bruker interferometer 2009 connected to the Swiss synchrotrond using a resolution
of 0.0007 cm−1 . In addition, the IR spectrum of CDBrClF has been measured at low temperature with our diode laser jet
setup in the ν5 region. The spectra of the two major isotopomers CD81 Br35 ClF and CD79 Br35 ClF have been analysed
within the ν5 (CCl-stretch), ν4 (CF-stretch) and ν3 (CDF-bend) regions. A detailed rovibrational analysis of these bands is
presented. The role for possible experiments in the experimental detection of molecular parity violation shall be discussed.
a M. Quack, Fundamental symmetries and symmetry violations in Handbook of High Resolution Spectroscopy, Vol. 1(Eds. M. Quack and F. Merkt),
Wiley, Chichester, New York 2011, 659-722, M. Quack, J. Stohner and M. Willeke, Annu. Rev. Phys. Chem. 2008, 59, 741, A. Bakasov, T.K. Ha, and
M. Quack, J. Chem. Phys. 1998, 109, 7263, R. Berger and M. Quack, J. Chem. Phys, 2000, 112, 3148.
b M. Quack and J. Stohner, Phys. Rev. Lett. 2000, 84, 3807, M. Quack and J. Stohner. J. Chem. Phys., 2003, 119, 11228.
c S. Albert, K. Keppler Albert and M. Quack, High Resolution Fourier Transform Infrared Spectroscopy in Handbook of High Resolution Spectroscopy,
Vol. 2 (Eds. M. Quack and F. Merkt), Wiley, Chichester, New York 2011, 965-1019, S. Albert and M. Quack, ChemPhysChem, 2007, 8, 1271-1281.
d S. Albert, K.K. Albert, Ph. Lerch and M. Quack, Faraday Discussions 2011, 150, 71-99.
152
TA05
CAVITY-ENHANCED PARITY-NONCONSERVING OPTICAL ROTATION IN Hg, Xe, AND I
15 min 9:56
L. BOUGAS, G. E. KATSORINAKIS, T. PETER RAKITZIS, Department of Physics, University of Crete, and
Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas 71110 HeraklionCrete, Greece.
Atomic parity-nonconservation (PNC) experiments provide a low-energy test of the Standard Model. However, atomic
PNC experiments have proved to be very difficult, typically taking at least 10-20 years to complete. In addition, the
measurements of anapole moments in Cs and Tl (the only such measurements to date, performed in the mid 1990s) appear
to be inconsistent with each other. Atomic PNC experiments on radioactive isotopes of Fr and Ra are underway at collider
facilities (TRIUMF and KVI Groningen, respectively), for which larger experimental signals are expected and several
isotopes are available. Here, we describe our recent proposals for the measurement of PNC optical rotation in metastable
Hg and Xe [1], and ground state I atoms [2]. A novel optical cavity is proposed which amplifies the optical rotation by
about 104 , and allows two signal reversals, therefore allowing room-temperature, table-top PNC experiments with large
experimental PNC signals, and rapid signal reversals. We discuss the experimental sensitivity to anapole moments for
odd-proton nuclei (in I) and odd-neutron nuclei (in Hg and Xe).
1 L. Bougas, G. E. Katsoprinakis, W. von Klitzing, J. Sapirstein, and T. P. Rakitzis, Phys. Rev. Lett 108, 210801
(2012).
2 G. E. Katsoprinakis, L. Bougas, T. P. Rakitzis, V. A. Dzuba and V. V. Flambaum, Phys. Rev. A (submitted)
http://arxiv.org/abs/1301.6947.
TA06
15 min 10:13
CHIRAL CAVITY RING-DOWN: ABSOLUTE MEASUREMENT OF OPTICAL ROTATION IN GASES AND LIQUIDS WITH SIGNAL REVERSALS
LYKOURGOS BOUGAS, G. E. KATSOPRINAKIS, T. P. RAKITZIS, Department of Physics, University of
Crete, and Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas 71110
Heraklion-Crete, Greece.
We demonstrate the absolute measurement of optical rotation using a four-mirror cavity-ring-down polarimetric setup.
A four-mirror bow-tie cavity allows counter-propagating laser beams, for which symmetry is broken with a longitudinal
magnetic field acting upon an intracavity magneto-optic window (producing a Faraday rotation θF ). A chiral sample is
introduced in one arm of the cavity, producing a chiral rotation ϕC . The different symmetry of the two rotations produces a
total rotation of (θF + ϕC ) for one laser beam, and (θF + ϕC ) for the counter-propagating beam. These rotations produce a
polarization beating in the cavity ring-down, of frequency ωCW and ωCCW for the clockwise and counter-clockwise beams,
respectively. Analysis of the difference (ωCW − ωCCW ) yields the chiral rotation angle ±ϕC , where the sign of the angle is
~ and yields2ϕ , allowing
determined by the sign of the applied magnetic field. Therefore, subtracting the signals using +B
C
the absolute determination of ϕC , without needing to remove the sample [1]. We demonstrate these absolute optical rotation
measurements for chiral gases (α-pinene) and chiral liquids.
This work is a proof-of-principle demonstration of the experimental setup proposed for the measurement of parity nonconserving optical rotation in atomic systems [1].
1 L. Bougas, G. E. Katsoprinakis, W. von Klitzing, J. Sapirstein, and T. P. Rakitzis, Phys. Rev. Lett 108, 210801
(2012).
Intermission
153
TA07
15 min 10:45
NEW PERSPECTIVES ON THE SEARCH FOR A PARITY VIOLATION EFFECT IN CHIRAL MOLECULES
F. AUGUSTE, S. K. TOKUNAGA, A. SHELKOVNIKOV, C. DAUSSY, A. AMY-KLEIN, C. CHARDONNET and B. DARQUIÉ, Laboratoire de Physique des Lasers, Université Paris 13, Sorbonne Paris Cité, CNRS,
F-93430, Villetaneuse, France.
Parity violation (PV) effects have so far never been observed in chiral molecules. Originating from the weak interaction,
PV should lead to frequency differences in the rovibrational spectra of the two enantiomers of a chiral molecule. However
the smallness of the effect represents a very difficult experimental challenge. We propose to compare the rovibrational
spectra (around 10 µm) of two enantiomers, recorded using the ultra-high resolution spectroscopy technique of Dopplerfree two-photon Ramsey interferometry in a supersonic molecular beam. With an alternate beam of left- and right-handed
molecules and thanks to our expertise in the control of the absolute frequency of the probe CO2 lasers, we should reach a
fractional sensitivity better around 10−15 (a few tens of millihertz), on the frequency difference between enantiomers a .
We will review our latest results on the high-resolution spectroscopy, either in cell or in a supersonic beam, of methyltrioxorhenium b , an achiral test molecule from which chiral derivatives fulfilling all the requirements for the PV test have been
synthesized c .
a B. Darquié, C. Stoeffler, A. Shelkovnikov, C. Daussy, A. Amy-Klein, C. Chardonnet, S. Zrig, L. Guy, J. Crassous, P. Soulard, P. Asselin, T. R. Huet,
P. Schwerdtfeger, R. Bast and T. Saue, Chirality 22, 870 (2010).
b C. Stoeffler, B. Darquié, A. Shelkovnikov, C. Daussy, A. Amy-Klein, C. Chardonnet, L. Guy, J. Crassous, T. R. Huet, P. Soulard and P. Asselin, Phys.
Chem. Chem. Phys. 13, 854 (2011).
c N. Saleh, S. Zrig, L. Guy, R. Bast, T. Saue, B. Darquié and J. Crassous, submitted to Phys. Chem. Chem. Phys. (2013).
TA08
TRAVELLING-WAVE DECELERATION OF HEAVY DIATOMIC MOLECULES
15 min
11:02
We have set up up a travelling-wave Stark-decelerator optimised for the deceleration and trapping of heavy diatomic
molecules. This decelerator is an important first step in the optimal preparation of heavy diatomic molecules for sensitive
studies of fundamental symmetries. The decelerator uses ring-shaped electrodes to create a moving trapping potential, that
can be brought to a standstill in the laboratory frame by electronic control. With such a device, a wide range of molecules
in the weak-field seeking part of excited rotational states can be decelerated and trapped. We demonstrate the working
principle of our method using SrF molecules, which are well suited to probe for parity violation.
TA09
DETECTING PARITY VIOLATION USING TRAPPED MOLECULES
15 min
11:19
We are preparing cold samples of SrF molecules for a measurement of parity violation. This molecule is typical for a group
of polar molecules that are sensitive probes for fundamental symmetries that can be Stark decelerated and laser cooled.
We combine Stark deceleration with laser cooling to create ultracold samples of these molecules. We will go over the
special opportunities offered by this group of molecules, and discuss the essential steps to make optimal use of the long
confinement time offered by a sample of molecules confined in a trap.
154
TA10
A SLOW SOURCE OF MOLECULES FOR HIGH RESOLUTION SPECTROSCOPY
15 min
11:36
MARINA QUINTERO-PÉREZ, PAUL JANSEN, THOMAS E. WALL, WIM UBACHS and HENDRICK L. BETHLEM, LaserLaB, Department of Physics and Astronomy, VU University Amsterdam, De
Boelelaan 1081, 1081 HV Amsterdam, The Netherlands.
We present experiments on decelerating and trapping ammonia molecules using a combination of a Stark decelerator and a traveling wave decelerator. In the traveling wave
decelerator a moving potential is created by a series of ring-shaped electrodes to which
oscillating high voltages are applied. By lowering the frequency of the applied voltages,
the molecules confined in the moving trap are decelerated and brought to a standstill.
As the molecules are confined in a true 3D well, this new kind of deceleration has practically no losses, resulting in a great improvement on the traditional Stark deceleration
techniques. The necessary voltages are generated by amplifying the output of an arbitrary wave generator using fast HV-amplifiers, giving us great control over the trapped
molecules. We illustrate this by experiments in which we adiabatically cool trapped NH3
and ND3 molecules and resonantly excite their motion. Our main motivation for this research is the possibility to use the traveling wave decelerator as a source of cold molecules
for a molecular fountain. Previous attempts to create a fountain using a Stark decelerator
were unsuccessful due to losses at low velocities and a complex lens-system for cooling
and collimating the slow beam. A traveling wave decelerator should solve both of these
issues.
TA11
15 min 11:53
NOVEL INFRARED COHERENT SOURCES AND TECHNIQUES FOR SPECTROSCOPIC TEST OF FUNDAMENTAL PHYSICS PRINCIPLES
P. CANCIO PASTOR, I. GALLI, G. GIUSFREDI, D. MAZZOTTI, and P. DE NATALE, Istituto Nazionale
di Ottica-Consiglio Nazionale delle Ricerche (INO-CNR), and European Laboratory for Non-linear Spectroscopy (LENS) Via N. Carrara 1, 50019 Sesto Fiorentino, Italy.
Recent achievements in high sensitivity and precision molecular spectroscopy in the mid-IR open new perspectives for
experiments looking for possible violations of the basic postulates in quantum mechanics or quantum electro-dynamics
in simple molecular systems. A new generation of hybrid infrared sources, including a direct link to optical frequency
comb synthesizers (OFCSs) is under developmenta. They provide metrological frequency precision and sensitivities that
have achieved record levels of tens of parts-per-quadrillion when appropriate spectroscopic techniques are implementedb,c .
Such very recent developments will be reviewed.
An example of possible application to the test of fundamental principles is attacking the symmetrization postulate (SP).
Actually, the requirement of symmetry of the wave function under exchange of identical particles has a striking demonstration in the spectra of molecules including identical nuclei. The basic idea of the spectroscopic tests is to search with
extremely high sensitivity for (weak) molecular lines involving the forbidden states. Since the early test of SP violation in
bosonic particles, 12 C16 O2 molecule has been considered a playground system. An upper limit of 10−11 to such violation
was measured more than one decade ago by our groupd. The recent developed spectroscopic techniqued,e measured a minimum detected CO2 gas pressures, in a 1-Hz bandwidth, of a few tens of femtobar, which could improve the previous test
by more than two orders of magnitude. Progress in high sensitivity spectroscopic measurements in view of new violation
tests will be reviewed, to investigate molecules with two and also three identical nuclei, like SO3 and NH3 .
a I.
Galli et al., Opt. Lett. 35, 3616 (2010). I. Ricciardi et al., Opt. Express 20, 9178 (2012). S. Borri, et al., Opt. Lett. 37, 1011 (2012).
Giusfredi et al., Phys. Rev. Lett. 104, 110801(2010).
c I. Galli et al., Phys. Rev. Lett. 107, 270802 (2011).
d D. Mazzotti et al., Phys. Rev. Lett. 86, 1919(2001).
b G.
155
TB. MINI-SYMPOSIUM: SPECTROSCOPY OF PLANETARY
ATMOSPHERES
Chair: PETER BERNATH, Old Dominion University, Norfolk, Virginia
TB01
INVITED TALK
30 min 8:30
THE ROLE OF SPECTROSCOPY IN RESEARCH ON THE NEUTRAL ATMOSPHERES OF THE OUTER SOLAR
SYSTEM
GLENN S. ORTON, JET PROPULSION LABORATORY, CALIFORNIA INSTITUTE OF TECHNOLOGY,
PASADENA, CA 91109.
Remote-sensing observations of Jupiter, Saturn, Uranus and Neptune, as well as Titan - Saturn’s largest satellite, and
the spectroscopic information required to interpret these observations play a pivotal role in the exploration of the atmospheres of the outer solar system. We rely on well-mixed constituents to derive temperatures unambiguously, with only the
collision-induced absorption and quadrupole transitions of H2 and CH4 in Jupiter and Saturn fulfilling that role. Condensate and chemically disequilibrated molecules (e.g. NH3 and PH3 ) act as indirect tracers that inform us of the strength of
vertical winds. Higher-order hydrocarbons are present in all these atmospheres and their abundances and distribution acts
as a tracer for stratospheric circulation and chemistry. The platforms on which planetary spectroscopy is done include a
variety of ground-based facilities that observe the planets from the visible through radio regions. Airborne facilities, such
as NASA’s SOFIA, together with Earth-proximal facilities in space, allow both increased sensitivity and wider spectral
access. Spectrometers on interplanetary missions have allowed us to examine the spatial and temporal variability of atmospheric properties that are not possible from the Earth. Several needs and challenges remain, and a constant dialog between
those in the planetary exploration community and laboratory spectroscopists and theorists has been and will continue to be
an important component of progress in atmospheric research. -
156
TB02
INTENSITY MODELING OF METHANOL IN THE TORSIONAL MANIFOLD
15 min 9:05
LI-HONG XU, Centre for Laser, Atomic and Molecular Sciences (CLAMS), Physics Department, University
of New Brunswick, 100 Tucker Park Road, Saint John, NB, Canada E2L 4L5; ISABELLE KLEINER, Laboratoire Interuniversitaire des Systemes Atmosphériques, CNRS et Universités Paris Diderot et Paris Est, 61 av.
Général de Gaulle, 94010, Créteil, France.
Methanol is a popular and very important molecule both in astrophysics and atmospheric science, for which reliable line
intensities have long been desired by the user communities. Because of the low barrier to the large-amplitude torsional
motion, the methanol spectrum is extremely rich and complicated, representing a significant challenge for global modeling.
Not until recent years has the torsional manifold of vt = 0, 1, and 2 levels been successfully globally modeled using a
modified version of the BELGI codea . The resulting global fit parameters were then used to predict line lists in the THz
region, employing both permanent dipole momentsb and torsional dependence of the dipole moments from ab initio resultsc
for the intensity calculations. However, recent direct intensity measurements based on Fourier transform spectra from JPLd
and THz measurements from the Ohio State Universitye call for improvement of the intensity model. Thus, we have
initiated enhanced modeling of the measured intensities in the torsional manifold using an extended set of dipole moment
parameters, including permanent (µa , µb ), torsionally dependent (µa3nγ , µb3nγ , µc3nγ ), and K and J dependent terms.
While we are hopeful that this will improve our intensity predictive power, we also foresee challenges in the modeling
for the A torsional species since a substantial body of the measured A doublet transitions exhibit either small asymmetry
splittings for low K and high J states or are barely to completely unresolved as K increases. The present status of this work
is that the existing database still needs some cleaning up to make it consistent with the new code. We hope to report our
early intensity fit results at the conference.
a Xu
et. al., J. Mol. Spectrosc. 251 (2008) p305.
& Lovas, J. Phys. Chem. Ref. Data 26 (1997) p17.
c Mekhtiev et. al., J. Mol. Spectrosc. 194 (1999) p171.
d Brauer et. al., JQSRT 113 (2012) p128.
e DeLucia, private communication.
b Xu
TB03
THZ SPECTROSCOPY OF DEUTERATED ETHANE
15 min 9:22
BRIAN J. DROUIN, SHANSHAN YU, JOHN C. PEARSON, LINDA R. BROWN, KEEYOON SUNG, Jet
Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Dr., Pasadena, CA 91109; PETER
GRONER, Department of Chemistry, University of Missouri-Kansas City, Kansas City, MO 64110-2499.
Over 200 rotational transition frequencies in ground vibrational state of C2 H5 D, with J < 38, were measured up to 1.6
THz with accuracies of 50-100 kHz and fitted to an effective Hamiltonian. These measurements extend the work of
Hirota et al., who measured and analyzed the millimeter-wave spectrum more that 30 years agoa and observed that the
relatively high barrier of 1007 cm−1 produced A − E splittings on the order of 10 MHz in the vibrational ground state.
The effective Hamiltonian fit to all data requires 17 parameters, including ρ, β, 11 rotational and distortion parameters, and
4 tunneling parameters. The experimentally determined value of ρ is 0.434308(19) and the primary tunneling parameter
ǫ1 is -24.7323(58) MHz. The data-set is limited by the vanishingly small dipole moment, such that we recorded rotational
R branch transitions up to 1.6 THz and rotational Q branch transitions up to 600 GHz in a three or six meter path with 0.2
Torr sample pressure. This data set is sufficient to locate all of the thermally populated energy levels of the ground state
up through the Boltzmann peak near J = 18, which may enable the assignment of the complex infrared spectrum in the
700-900 cm−1 range.
a
Hirota et al. J. Molec. Spectrosc. 89, 285 (1981).
157
TB04
15 min 9:39
OZONE RECOVERY IN THE PRESENCE OF O2 (a ∆) FOR ATMOSPHERIC STUDIES
1
MICHAEL C. HEAVEN, Department of Chemistry, Emory University, Atlanta, GA 30322; VALERIY N.
AZYAZOV, P.N. Lebedev Physical Institute, Samara Branch, Samara, Russia, 443029.
Rapid quenching of O2 (a1 ∆) in O(3 P)/O2 /O3 mixtures has been observed using 248 nm laser photolysis of ozone to
produce oxygen atoms and O2 (a1 ∆) molecules. Collisional removal of O2 (a1 ∆) was found to be correlated with the
presence of O atoms. The kinetics indicate that vibrationally excited ozone is an important O2 (a1 ∆) quenching agent in
O(3 P)/O2 /O3 systems. The impact of this quenching channel on the O2 (a1 ∆) and O3 levels in the atmosphere will be
discussed.
Intermission
TB05
Journal of Molecular Spectroscopy Review Lecture
30 min
10:15
EXOMOL: MOLECULAR LINE LISTS FOR EXOPLANET AND OTHER ATMOSPHERES
JONATHAN TENNYSON, Department of Physics and Astronomy, University College London, London,
WC1E 6BT, UK.
Spectral characterization of astrophysical objects cool enough to form molecules in their atmospheres (cool stars, extrosolar
planets and planetary discs) requires considerable amounts of fundamental molecular data. The existing molecular line lists
(with some exceptions) are generally not sufficiently accurate and complete. The ExoMol project is actively generating
comprehensive line lists for all molecules likely to be observable in exoplanet atmospheres in the foreseeable future. This
is a huge undertaking which will mean providing in excess of 1011 spectral lines for a large variety of molecular species,
see Tennyson and Yurchenko (Mon. Not. R. Astron. Soc., 425, 21 (2012))
The physics of molecular absorptions is complex and varies between different classes of absorbers. The project is therefore be divided into following topics (a) diatomic, (b) triatomics, (c) tetratomics, (d) methane and (e) larger molecules.
Special techniques are being developed to treat each case. The majority of diatomic systems to be tackled are open shell
species involving a transition metal atom; the opacity is provided by the transitions between the many low lying electronic
states of the system. The calculation of rotation-vibration line lists for closed-shell triatomic systems is now relatively
straightforward provided enough care is taken in deriving the potential energy and dipole surfaces. An H2 S line list is
nearing completion and studies on C3 have started. Accurate rotation-vibration line lists for hot tetratomic molecules such
as ammonia (complete), phosphine (nearing completion), acetylene (initial study published), hydrogen peroxide (initial
study complete), SO3 (room temperature line list complete) and formaldehyde, test what is computationally possible at
present. An inital line list for hot (1000 K) methane has been completed and is being improved. Work on systems larger
than this is just commencing. Data from this project can be accessed at www.exomol.com.
TB06
15 min
A NEW GLOBAL FIT FOR
17
10:50
O ENRICHED CO2
BEN M. ELLIOTT, CHARLES E. MILLER, Jet Propulsion Laboratory, California Institute of Technology,
4800 Oak Grove Drive, M/S 233-300, Pasadena, CA 91109.
Ground-, air- and space-based remote sensing of atmospheric carbon dioxide (CO2 ) require accurate and complete spectroscopic characterization; however, these stringent requirements have been satisfied only for a few absorption bands of the
main 16 O-12 C-16 O (626) isotopologue, and significant deficiencies exist in most spectral regions. This paucity in characterization is especially prominent in the case of the rarer isotopologues, particularly the 17 O enriched species. As part of
our systematic investigation of CO2 spectroscopy, we report a new global fit for the 16 O-12 C-17 O (627) and 17 O-12 C-17 O
(727) isotopologues that includes a critical evaluation of all previously reported data, as well as new data to improve the
fit accuracy and coverage. The global, interrelated nature of the present fit also enables accurate predictions of as yet
unmeasured bands. The fit is used to produce a new catalog of predicted line positions and uncertainties for use in remote
sensing retrievals.
158
TB07
15 min
SEMI-EMPIRICAL DIPOLE MOMENT FUNCTION OF X Σ CO
1
+
11:07
a
GANG LI, IOULI E. GORDON and LAURENCE S. ROTHMAN, Harvard-Smithsonian Center for Astrophysics, Atomic and Molecular Physics Division, Cambridge MA 02138, USA.
A new dipole moment function (DMF) for the ground X 1 Σ+ electronic states of carbon monoxide (CO) has been obtained
using a direct fit approach that fits the best available and appropriately weighted experimental line intensity data for individual ro-vibrational transitions. This method was recently successfully applied to HF, HCl, HBr and HI moleculesa .
The new dipole moment function benefits from the use of new accurate and extensive experimental data. Also our method
allows proper weighting of the data as well as not being dependent on the amount of measured transitions within a band.
Combining the newly developed (taking into account the most recent experiments) empirical potential energy functions
and the DMF, line positions and line intensities of CO and their isotopologues have been calculated numerically using
program LEVELb . In addition, new semi-empirical algorithms for assigning line-shape parameters and line shifts for these
species have been developed. Using these improvements, new line lists for CO were created to update the HITRANc and
HITEMPd spectroscopic database.
a This
effort has been supported by NASA through EOS grant NNX11AF91G and Planetary Atmospheres grant NNX10AB94G.
Li, I.E. Gordon, R.J. Le Roy, P.G. Hajigeorgiou, J.A. Coxon, P.F. Bernath, and L.S. Rothman, “Reference spectroscopic data for Hydrogen
Halides. Part I: Construction and Validation of the Ro-vibrational Dipole Moment Functions,” JQSRT 2013 (In Press).
b R. Le Roy, “LEVEL. 8.0 ed2007” University of Waterloo Chemical Physics Research Report CP-663 (2007).
c L.S. Rothman, I.E. Gordon, A. Barbe, D.Chris Benner, P.F. Bernath, et al, “The HITRAN 2008 Molecular Spectroscopic Database,” JQSRT 110,
532-572 (2009).
d L.S. Rothman, I.E. Gordon, R.J. Barber, H. Dothe, R.R. Gamache, A. Goldman, V. Perevalov, S.A. Tashkun, and J. Tennyson, “HITEMP, the
high-temperature molecular spectroscopic database,” JQSRT 111, 2139-2150 (2010).
a G.
TB08
15 min
CHARACTERIZATION OF OZONE PROFILES DERIVED FROM AURA TES AND OMI RADIANCES
11:24
DEJIAN FU, JOHN R. WORDEN, SUSAN S. KULAWIK, KEVIN V. BOMAN AND VIJAY NATRAJ,
Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109; XIONG LIU, HarvardSmithsonian Center for Astrophysics, Cambridge, Massachusetts 02138, USA.
We present satellite based ozone profile estimates derived by combining radiances measured at thermal infrared (TIR)
wavelengths from the Aura Tropospheric Emission Spectrometer (TES) and ultraviolet (UV) wavelengths measured by
the Aura Ozone Monitoring Instrument (OMI). The advantage of using these combined wavelengths and instruments for
sounding ozone over either instrument alone is improved sensitivity near the surface as well as the capability to consistently resolve the lower troposphere, upper troposphere, and lower stratosphere for scenes with varying geophysical states.
For example, the vertical resolution for ozone estimates from either TES or OMI vary strongly by surface albedo and
temperature and typically provide 1.6 degrees-of-freedom for signal (DOFS) for TES or less than 1 DOFS for OMI in
the troposphere. The combination typically provides 2 DOFS in the troposphere with approximately 0.4 DOFS for near
surface ozone (surface to 700 hPa). We evaluate these new ozone profile estimates with ozonesonde measurements and
find that calculated errors for the joint TES and OMI ozone profile estimates are in approximate agreement with actual
errors as derived by the root-mean-square difference between the ozonesondes and the joint TES/OMI ozone estimates.
We find that the vertical resolution of the joint TES/OMI ozone profile estimate is sufficient for quantifying variations in
near-surface ozone with a precision of 26 % (15.6 ppb) and a bias of 9.6 % (5.7 ppb).To further improve the quality of
ozone measurements using multiple spectral regions, next generation of ozone spectroscopic parameters should mitigate
the existing discrepancy among different spectral regions (microwave, thermal infrared, visible and ultraviolet).
159
TB09
15 min 11:41
MODELING THE SPECTRUM OF THE 2ν2 and ν4 STATES OF AMMONIA TO EXPERIMENTAL ACCURACY
Oak Grove Dr., Pasadena, CA 91109, USA.
The vibrational spectrum of ammonia has received an enormous amount of attention due to its prevalence in hot exo-planet
atmospheres and persistent challenges in assigning and modeling highly excited and often highly preturbed states, resulting
from strong coupling between the large amplitude inversion and the other small amplituded vibrations. Previously, only
the ground and ν2 positions could be modeled to experimental accuracy using effective Hamiltonians.a However, problems
persist in calculation of transition intensities especially in the “forbidden" ∆K = 3 bands. Several previous attempts
to analyze the 2ν2 and ν4 failed to model both the microwave and infrared transitions to experimental accuracy.bc We
report comprehensive measurements of the pure rotational spectrum in the 2ν2 , ν4 and 2ν2 − ν4 bands. Over 180 new
frequency measured transitions and several thousand infrared transitions have been assigned in the microwave spectrum,
in a long path, room temperature, spectrum from SOLEIL, and in an RF discharge emission spectrum also from SOLEIL.
The new data has been combined with all the previously published high resoloution data. We report a global analysis of
the pure rotation in 2ν2 and ν4 , the difference band 2ν2 − ν4 , the hot bands 2ν2 − ν2 and ν4 − ν2 , the 2ν2 overtone, and
the ν4 fundamental. Experimental accuracy has been achieved in a fit of all the data with stated experimetal uncertainties.
Achieving experimental accuracy required inclusion of a number of terms in the effective Hamiltonian that were neglected
in previous work. These terms have also been neglected in the analysis of higher lying states suggesting that the inversionrotation-vibration spectrum of ammonia may be far more tractable to effective Hamiltonians than previously believed.
a Yu,
Pearson, Drouin, Sung, Pirali, Vervoet, Martin-Drumel, Endres, Shiraishi, Kobayashi, and Matsushima, J. Chem. Phys. 133 (2010) 174317.
Kleiner, Tarrago, Brown, Margolis, Poynter, Pickett, Fouchet, Drossart, and Lellouch, J. Mol. Spectrosc. 203 (2000) 285-309.
c Sasada, Endo, Hirota, Poynter, and Margolis, J. Mol. Spectrosc. 151 (1992) 33-53.
b Cottaz,
160
TC. MICROWAVE
Chair: VADIM ILYUSHIN, Institute of Radio Astronomy NASU, Khazkov, Ukraine
TC01
10 min 8:30
ROTATIONAL SPECTRA AND ANALYSIS OF THE ARGON-MONOFLUOROPYRIDINE VAN DER WAALS COMPLEXES
MAHDI KAMAEE, MING SUN AND JENNIFER VAN WIJNGAARDEN, Department of Chemistry, University of Manitoba, Winnipeg MB R3T 2N2 Canada.
Chirped pulse Fourier transform microwave (FTMW) spectra of the van der Waals complexes of 2-fluoropyridine and 3fluoropyridine with argon were serendipitously observed from 8-18 GHz while studying the pyridine monomers in 2011.
These initial observations were used as a guide to measure the spectra of the complexes between 4 and 26 GHz using
our Balle-Flygare FTMW instrument. With the higher resolution instrument, the 14 N quadrupole hyperfine structure was
observed and analyzed. Based on our ab initio calculations (MP2/6-311++G(2d 2p)), the observed rotational spectra are
consistent with a geometry such that the argon atom lies over the plane of pyridine within several degrees of the c-axis of
the ring. The center of mass separation between the two moieties is between 3.5 and 3.6 Å.
TC02
15 min 8:42
BROADBAND CHIRPED-PULSE FOURIER TRANSFORM MICROWAVE SPECTROSCOPY AND MOLECULAR
STRUCTURE OF THE ARGON-1-CHLORO-1-FLUOROETHYLENE COMPLEX
MARK D. MARSHALL AND HELEN O. LEUNG, Department of Chemistry, Amherst College, P.O. Box
5000, Amherst, MA 01002-5000.
Previous studies of argon complexes with fluoroethylenes have revealed a preference for a geometry that maximizes the
contact of the argon atom with heavy atoms on the fluoroethylene.a We have observed a continuation of this trend when
one of the fluorine atoms is replaced by chlorine. As part of a systematic study of the effect of chlorine substitution
on intermolecular interactions, we have examined the argon-1-chloro-1-fluoroethylene complex, and obtained the 5.6 –
18.1 GHz chirped-pulse Fourier transform microwave spectrum of this species. Transitions for both the 35 Cl and 37 Cl
isotopologues are observed and analyzed to provide geometric parameters for this non-planar complex. The structure is
found to be similar to those of analogous complexes and agrees well with ab initio predictions.
a Z.
Kisiel, P.W. Fowler, and A.C. Legon, J. Chem. Phys. 95, 2283 (1991).
TC03
15 min 8:59
MICROWAVE SPECTRA AND MOLECULAR STRUCTURES OF 2-CHLORO-1,1-DIFLUOROETHYLENE AND ITS
COMPLEX WITH ARGON
JOSEPH P. MESSINGER, GREGORY S. KNOWLTON, KATHRYN M. SUNDHEIM, HELEN O. LEUNG,
AND MARK D. MARSHALL, Department of Chemistry, Amherst College, P.O. Box 5000, Amherst, MA
01002-5000.
Chirped-pulse and Balle-Flygare spectrometers are used to obtain Fourier transform microwave spectra of 2-chloro-1,1difluoroethylene and its complex with argon from 5.5 to 21.0 GHz, allowing for the geometries of both species to be
determined. A total of six isotopologues are observed each for the monomer and dimer, including the most abundant
species, the singly-substituted 37 Cl and two singly-substituted 13 C isotopologues in natural abundance, and deuterated
versions of both the 35 Cl and 37 Cl species using an isotopically enriched sample. Similar to the previously studied argonhaloethylene complexes, the argon shows a preference for close contact with heavier atoms. Tunneling of the argon between
two equivalent non-planar structures, similar to that in argon-cis-1,2-difluoroethylene, is not observed in this complex.
161
TC04
15 min 9:16
ROTATIONAL SPECTRA OF THE TRIFLUORO ETHANOL (TFE) -WATER CLUSTERS AND THE TFE DIMERS
JAVIX THOMAS, YUNJIE XU, Department of Chemistry, University of Alberta, Edmonton, AB, T6G 2G2,
Canada.
TFE is an important organic solvent. TFE and water are often used as co-solvents in the studies of protein folding process.
Therefore it is very important to understand the interactions of TFE with water and itself in great detail. We have studied the
complexes of TFE with water and with itself using high level ab-initio calculations and rotational spectroscopy. Broadband
rotational spectra of TFE and TFE+water in helium have been obtained using a chirped pulse Fourier transform microwave
(FTMW) spectrometer. The rotational spectra of the lowest energy conformers of the TFE-water complexes and the
TFE dimer are assigned for the first time. The final frequency measurements have been done with a cavity based FTMW
spectrometer. Some interesting tunnelling splittings have been observed in the rotational spectra of the TFE-water complex.
Extensive isotopic studies of H2O, D2O and DHO have also been performed to get more insight into the tunneling motion
and structure of the TFE-water complex.
TC05
15 min 9:33
STRUCTURE FOR THE PROPIOLIC ACID - FORMIC ACID COMPLEX FROM MICROWAVE SPECTRA FOR
MULTIPLE ISOTOPOLOGUES a
STEPHEN G. KUKOLICH, ERIK G. MITCHELL, SPENCER J. CAREY, MING SUN, and
BRYAN M. SARGUS, Department of Chemistry and Biochemistry, The University of Arizona, Tucson,
Arizona 85721..
New microwave spectra were measured to obtain rotational constants and centrifugal distortion constants for the
DCCCOOH—HOOCH and HCCCOOD—DOOCH isotopologues. Transitions were measured in the 4.9-15.4 GHz range,
providing accurate rotational constants which, combined with previous rotational constants allowed an improved structural
fit for the propiolic acid - formic acid complex. The new structural fit yields orientations for both the propiolic and formic
acid monomers in the complex and more accurate structural parameters describing the hydrogen bonding. The structure is
planar, with a positive inertial defect of ∆ = 1.33 amu Å2 .The experimental structure exhibits a greater asymmetry for the
two hydrogen bond lengths than was obtained from the ab initio mp2 calculations.The average of the two hydrogen bond
lengths is R(exp) = 1.76 Å, in good agreement with R(theory) = 1.72 Å.
a Supported
TC06
15 min 9:50
THE EFFECT OF PROTIC ACID IDENTITY ON THE STRUCTURES OF COMPLEXES WITH VINYL CHLORIDE:
FOURIER TRANSFORM MICROWAVE SPECTROSCOPY AND MOLECULAR STRUCTURE OF THE VINYL
CHLORIDE-ACETYLENE COMPLEX
HELEN O. LEUNG, MARK D. MARSHALL, AND FAN FENG, Department of Chemistry, Amherst College,
P.O. Box 5000, Amherst, MA 01002-5000.
In all previous examples of complexes formed between protic acids and haloethylenes, we have observed similar modes
of binding regardless of the specific identity of the acid, HF, HCl, or HCCH. Although details of the structures, such
as hydrogen bond length and amount of deviation from linearity, do reflect the strength of the interaction and show clear
correlations with the gas-phase acidity, the complexes of a given haloethylene with any of the acids have identical structural
motifs. As part of a systematic study of the effects of chlorine substitution on intermolecular interactions of haloethylenes,
we have studied the complexes of vinyl chloride with both HF and HCCH. The HF complex, reported last year, has
a geometry with HF interacting across the double bond of vinyl chloride and forming a secondary interaction with the
hydrogen cis to the chlorine atom. We have obtained the broadband, chirped-pulse and narrow band, Balle-Flygare Fourier
transform microwave spectra of the vinyl chloride-HCCH complex. The spectra indicate that HCCH locates at one end of
the vinyl chloride with the secondary interaction occurring with the geminal hydrogen atom.
Intermission
162
TC07
15 min 10:20
THE MICROWAVE STUDIES OF GUAIACOL (2-METHOXYPHENOL) ISOTOPOLOGUES AND VAN DER WAALS
COMPLEXES
RANIL M. GURUSINGHE, ASHLEY FOX, and MICHAEL J. TUBERGEN, Department of Chemistry, Kent
State University, Kent, OH 44242.
The microwave spectrum of one conformer of guaiacol, 2-methoxyphenol, was recorded in the 12-21 GHz range. Fifty two
rotational transitions were fitted to the lowest energy ab initio structure computed with Hatree-Fock method using the 6311++G(d,p) basis set. The fitted rotational constants are: A= 2607.0664(6) MHz, B= 1560.7967(2) MHz, C= 982.8721(1)
MHz. Microwave spectra were recorded for each of seven unique 13 C isotopomers and the deuterated hydroxyl isotopomer.
Quantum chemical calculations and the spectral analysis indicate that the observed conformer is the anti − syn form of
guaiacol. Progress on the assignment of the Argon-guaiacol complex and water-guaiacol complex will also be presented.
TC08
15 min 10:37
AN IMPROVED CHIRPED PULSE FTMW ANALYSIS OF THE STRUCTURES OF PHENOL DIMER AND TRIMER
NATHAN A. SEIFERT, CRISTÓBAL PÉREZ, AMANDA L. STEBER, DANIEL P. ZALESKI, JUSTIN L.
NEILL, BROOKS H. PATE, Department of Chemistry, University of Virginia, McCormick Rd., Charlottesville,
VA 22904-4319; ALBERTO LESARRI, Departamento de Química Física y Química Inorgánica, Facultad de
Ciencias, Universidad de Valladolid, E-47001 Valladolid, Spain.
With the recent improvements for chirped pulse FTMW (CP-FTMW) spectroscopy between 2-18 GHz, substitution structures of molecules and clusters with more than 10 heavy atoms are becoming routine. While previous CP-FTMW results for
phenol dimer reported at this conference by Steber et al.a necessitated reduced-band measurements in order to achieve the
sensitivity to detect the carbon isotopologues, the latest improvements for the 2-8 GHz arrangement have enabled full band
detection of all 12 13 C and 2 18 O isotopologues of phenol dimer in natural abundance, with improved fits for all detected
species. In addition, the added sensitivity of this new 2-8 GHz configuration has enabled a full carbon substitution structure of phenol trimer. The experimental structure of phenol trimer, in agreement with the M06-2X/6-311++g(d,p) ab initio
structure, is a C3 oblate symmetric top with 21 heavy atoms; however, all possible isotopic substitutions are off-symmetry
axis, so the resulting detected isotopologues have been fit as c-type prolate asymmetric tops. Use of Kraitchman′s equations for structural determination of a symmetric top molecule require some assumptions from the ab initio structure for
the complete rs structure of the trimer. A detailed summary of these methods, as well as the microwave results for both
species, will be presented.
a A.
L. Steber, J. L. Neill, D. P. Zaleski, B. H. Pate, A. Lesarri. 67th OSU Int. Symp. On Mol. Spectrosc., Columbus, OH, 2012, MH13.
163
TC09
10 min 10:54
OLIGOMERS BASED ON A WEAK HYDROGEN BOND NETWORK: THE ROTATIONAL SPECTRUM OF THE
TETRAMER OF DIFLUOROMETHANE
GANG FENG, LUCA EVANGELISTI, and WALTHER CAMINATI, Dipartimento di Chimica "G. Ciamician" dell’Università, Via Selmi 2, I-40126 Bologna, Italy; IVO CACELLI, and LAURA CARBONARO,
Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Risorgimento 35, I-56126 Pisa,
Italy; GIACOMO PRAMPOLINI, Istituto per i Processi Chimico-Fisici (IPCF-CNR), Area della Ricerca,
Via G. Moruzzi 1, I-56124 Pisa, Italy.
Following the investigation of the rotational spectra of three conformers (so-called “book”, “prism” and “cage”) of the
water hexamer, and of some other water oligomers, a we report here the rotational spectrum of the tetramer of a freon
molecule.
The pulse jet Fourier transform microwave (pj-FTMW) spectrum of an isomer of the difluoromethane tetramer has been
assigned. This molecular system is made of units of a relatively heavy asymmetric rotor, held together by a network
of weak hydrogen bonds. The search of the rotational spectrum has been based on a high-level reference method, the
CCSD(T)/CBS protocol.
It is interesting to outline that the rotational spectrum of the water tetramer was not observed, probably because the minimum energy structures of this oligomer is effectively nonpolar in its ground states, or because of high energy tunnelling
splittings.
The rotational spectra of the monomer, dimer, trimer and tetramer of difluoromethane have been assigned in 1952, b 1999,
c
2007, d and 2013 (present work), with a decreasing time spacing between the various steps, looking then promising for a
continuous and rapid extension of the size limits of molecular systems accessible to MW spectroscopy.
a C.
Pérez, M. T. Muckle, D. P. Zaleski, N. A. Seifert, B. Temelso, G. C. Shields, Z. Kisiel, B. H. Pate, Science 336 (2012) 897.
R. Lide, Jr., J. Am. Chem. Soc. 74 (1952) 3548.
c W. Caminati, S. Melandri, P. Moreschini, P. G. Favero, Angew. Chem. Int. Ed. 38 (1999) 2924.
d S. Blanco, S. Melandri, P. Ottaviani, W. Caminati, J. Am. Chem. Soc. 129 (2007) 2700.
b D.
TC10
ROTATIONAL SPECTRA OF ADDUCTS OF FORMALDEHYDE WITH FREONS
15 min
11:06
GOU QIAN, GANG FENG, LUCA EVANGELISTI, and W. CAMINATI, Dipartimento di Chimica
"G. Ciamician" dell’Università, Via Selmi 2, I-40126 Bologna, Italy; MONTSERRAT VALLEJO LÓPEZ,
ALBERTO LESARRI, Departamento de Quimica Fisica y Quimica Inorganica, Facultad de Ciencias, Universidad de Valladolid, E-47011 Valladolid, Spain; EMILIO COCINERO, Departamento de Quimica Fisica,
Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco, E-48080 Bilbao, Spain.
The rotational spectra of three 1:1 complexes of formaldehyde (H2 CO) with freons, i.e. difluoromethane (CH2 F2 ), fluorochloromethane (CH2 FCl) and trifluorochloromethane (CF3 Cl), have been observed and assigned using pulsed jet Fourier
transform microwave technique. Several isotopologues (including some 13 C species) have been measured in natural abundance. The tunnelling splittings have been measured in the first two adducts with relative intensity 1:3, due to the internal
rotation of the formaldehyde moity along its symmetry axis. The barriers to this motion have been estimated by using a
flexible model. For the latter two complexes, each of transition displays the hyperfine structures due to the quadrupolar
effects of 35 Cl (37 Cl) nucleus. The dissociation energy has been estimated within the pseudo-diatomic approximation for
all three complexes.
164
TC11
MICROWAVE SPECTROSCOPIC INVESTIGATIONS
CH2 F2 · · · PROPYNE AND CH2 ClF· · · PROPYNE
OF
THE
C–H· · · π
15 min 11:23
CONTAINING COMPLEXES
REBECCA A. PEEBLES, SEAN A. PEEBLES, CORI L. CHRISTENHOLZ, ANTHONY A. ERNST, and
YASSER J. DHAHIR, Department of Chemistry, Eastern Illinois University, 600 Lincoln Ave., Charleston, IL
61920.
The spectra of the CH2 F2 · · · propyne and CH2 ClF· · · propyne complexes have been studied by chirped-pulse and resonant cavity Fourier-transform microwave spectroscopy and by ab initio calculations at the MP2/6-311++G(2d,2p) level.
Both complexes contain C–H· · · π contacts, with the halogen atoms angled towards the methyl group end of the propyne.
While CH2 F2 · · · propyne has Cs symmetry, CH2 ClF· · · propyne has C1 symmetry, with the fluorine and chlorine atoms
straddling the propyne.
Investigation of four single 13 C and the DC≡CCH3 isotopologues in CH2 F2 · · · propyne has allowed a detailed structural
determination, while only the 35 Cl and 37 Cl isotopologues have so far been assigned for CH2 ClF· · · propyne. Experimental
data will be compared with ab initio results and with the analogous acetylene complexes, both of which have Cs symmetry
structures, with double C–H· · · π interactions.
TC12
10 min 11:40
OBSERVATION OF A C–H· · · AROMATIC INTERACTION IN THE FLUOROBENZENE· · · HCCH WEAKLY
BOUND COMPLEX
NATHAN W. ULRICH, SEAN A. PEEBLES, REBECCA A. PEEBLES, and YASSER J. DHAHIR, Department of Chemistry, Eastern Illinois University, 600 Lincoln Ave., Charleston, IL 61920; NATHAN A.
SEIFERT, CRISTÓBAL PÉREZ, and BROOKS H. PATE, Department of Chemistry, University of Virginia,
McCormick Rd., PO Box 400319, Charlottesville, VA 22904.
Chirped-pulse Fourier-transform microwave (CP-FTMW) spectroscopy has been used to determine the structure of the
C6 H5 F· · · HCCH weakly bound complex. Assignment of spectra for the parent and all six unique 13 C isotopologues
in natural abundance has allowed a full structure determination, using both Kraitchman substitution and least-squares
methods. The acetylene lies nearly perpendicular to the fluorobenzene ring, approximately above the ring center, and in
the dimer ab symmetry plane. There is a slight tilt of the hydrogen atom nearest the fluorobenzene away from the carbon
atom bonded to the fluorine. The distance between the centers of mass of the two monomers is approximately 4.18(1)Å,
with C–H· · · C distances of between 2.81(1)Å and 2.92(1)Å. The experimentally determined structure is in reasonable
agreement with the minimum energy configuration from an MP2/6-311++G(2d,2p) ab initio calculation. Comparison will
also be made with similar complexes of aromatic compounds with potential hydrogen bond donors.
165
TD. RADICALS AND IONS
Chair: YUAN-PERN LEE, National Chiao Tung University, Hsinchu, Taiwan
TD01
THE ROLES OF ATOMIC OXYGEN AND NITRIC OXIDE IN LOW TEMPERATURE PLASMAS
15 min 8:30
SHERRIE S. BOWMAN, DAVID BURNETTE, IGOR V. ADAMOVICH, and WALTER R. LEMPERT, M.A.
Chaszeyka Non-Equilibrium Thermodynamics Laboratory, The Ohio State University, Columbus, Ohio 43210..
Nitric oxide, NO, and oxygen, O, concentrations have been experimentally measured using one-photon and two-photon
laser induced fluorescence, respectively, as a function of time after a nanosecond pulsed plasma discharge. The relative
behavior of these two species is fundamentally different than that predicted using the extended Zeldovich Mechanism. A
plasma chemistry kinetic model sensitivity analysis has been conducted to determine the dominate reactions involved. The
spectra, concentrations, and kinetic modeling predictions will be discussed.
TD02
15 min 8:47
SUB-DOPPLER SPECTROSCOPY OF trans-HOCO RADICAL IN THE OH STRETCHING MODE
CHIH-HSUAN CHANG, GRANT BUCKINGHAM, and DAVID J. NESBITT, JILA, National Institute of
Rovibrational spectroscopy of the fundamental OH stretching mode of trans-HOCO radical has been studied via subDoppler high resolution infrared laser absorption in a discharge slit-jet expansion. The trans-HOCO radical is formed by
discharge dissociation of H2 O to form OH, which then combines with CO and cools in the Ne expansion to a rotational
temperature of 16 K. Rigorous assignment of both a-type and b-type spectral transitions is made possible by 2-line combination differences from microwave studiesa , with full rovibrational analysis of the spectrum based on a Watson asymmetric
top Hamiltonian. Additionally, fine structure splittings of each line due to electron spin are completely resolved and thus
permitting all three ǫaa , ǫbb , ǫcc spin rotation constants to be experimentally determined. Furthermore, the ratio of transition dipole moment along the molecule A and B axis is determined to be µa /µb = 1.72(5), in agreement with quantum
theoretical calculations(1.85).
a T.
Oyama,W Funato, Y. Sumiyoshi,and Y. Endo, J. Chem. Phys. 134, 174303.
TD03
15 min 9:04
e-X
e TRANSITION OF ISOPROPOXY RADICAL
VIBRONIC ANALYSIS FOR B
RABI CHHANTYAL-PUN and TERRY A. MILLER, Laser Spectroscopy Facility, Department of Chemistry,
The Ohio State University, 120 W. 18th Avenue, Columbus OH 43210.
Alkoxy radicals are important intermediates in combustion and atmospheric chemistry. Alkoxy radicals are also of sige and A
e states.
nificant spectroscopic interest for the study of Jahn Teller and pseudo Jahn Teller effects, involving the X
The Jahn Teller effect has been studied in methoxy. Substitution of one or two hydrogens by methyl groups transforms
the interaction to a pseudo Jahn Teller effect in ethoxy and isopropoxy. Previously, moderate resolution scans have been
e-X
e and B
e-A
e transition systems, the latter observable at higher temperature. These measurements have
obtained for B
e
e
shown that the X and A states of isopropoxy are separated by only 60.7(7) cm−1 which indicates a strong pseudo Jahn
e state. Such pseduo Jahn Teller coupling should also introduce additional bands into the B
e-X
e specTeller effect in the X
trum and a number of weaker transitions have been observed which may be caused by such effects. In this talk we present
e-X
e transition based on the experimental results and also the results from recent quantum
a vibronic analysis for the B
chemistry calculations.
166
TD04
15 min 9:21
ANALYSIS OF THE ROTATIONAL STRUCTURE OF B̃ A ← X̃ A TRANSITION OF ISOPROPOXY RADICAL:
ISOLATED STATE vs. COUPLED STATES MODEL
2
′
2
′
DMITRY G. MELNIK, and TERRY A. MILLER, Laser Spectroscopy Facility, Department of Chemistry, The
Ohio State University, 120 W. 18th Avenue, Columbus, Ohio 43210; JINJUN LIU, Department of Chemistry,
University of Louisville, 2320 South Brook Street, Louisville, Kentucky 40292.
Isopropoxy radicals are reactive intermediates in atmospheric and combustion chemistry. From the theoretical point of
view, they represent an extreme case of “isotopically” substituted methoxy radicals with two methyl groups playing the
role of heavy hydrogen isotopes. Previouslya the rotationally resolved spectra of B̃ 2 A′ ← X̃ 2 A′ electronic transition were
successfully analyzed using a simple effective rotational Hamiltonian of the isolated X̃ and B̃ states. However, a number
of the experimentally determined parameters appeared dramatically inconsistent with the quantum chemistry calculations
and theoretical predictions based on the symmetry arguments.
Recently, we analyzed these spectra using a coupled two state model, which explicitly includes interactions between the
ground X̃ 2 A′ state and low-lying excited Ã2 A′′ state. In this presentation we will discuss the results of this analysis and
compare the parameters of both models and their physical significance.
a D.
G. Melnik, T. A. Miller and J. Liu, TI15, 67th Molecular Spectroscopy Symposium, Columbus, 2012
TD05
15 min 9:38
HIGH-RESOLUTION LASER-INDUCED FLUORESCENCE SPECTROSCOPY OF CYCLOHEXOXY: ROTATIONAL
AND FINE STRUCTURE OF MOLECULES IN NEARLY DEGENERATE ELECTRONIC STATES
JINJUN LIU, Department of Chemistry, University of Louisville, 2320 S. Brook St., Louisville, Kentucky
40292.; DMITRY G. MELNIK, and TERRY A. MILLER, Laser Spectroscopy Facility, Department of Chemistry, The Ohio State University, 120 W. 18th Ave., Columbus, Ohio 43210.
The previously obtained B̃ 2 A′ − X̃ 2 A′′ and B̃ 2 A′ − Ã2 A′ laser-induced fluorescence (LIF) spectra of jet-cooled cyclohexoxy radical (c-C6 H11 O)a have been analyzed and simulated using the coupled-two-state model presented in the preceding
talk. The rotational and fine structure of the nearly degenerate X̃ 2 A′′ and Ã2 A′ states is reproduced using one set of
molecular constants including rotational constants, spin-rotation constants, effective spin-orbit constants (aζe d) and the
vibronic energy separation between the two states (∆E). While the energy level structure could be reproduced by only
effective spin-rotation constants (without the spin-orbit constant), the spin-orbit interaction introduces transitions that have
no intensity using the separate-states asymmetric rotor model. Rotational and fine-structure analysis using the two-state
model has proven to be an effective method to separate the first order electron-spin-molecular-rotation constants from the
effective spin-rotation constants, and to decouple the spin-orbit splitting (aζe d) and the vibronic energy separation (∆E),
both of which contribute to the experimentally observed energy separation between the two coupled states (∆E Ã−X̃ ).
Isopropoxy (discussed in the preceding talk), cyclohexoxy, and other molecules in nearly degenerate electronic states provide unique cases bridging the gap from symmetrically degenerate states, e.g., ground X̃ 2 E state of methoxy, and the
Born-Oppenheimer limit of unperturbed electronic states.
a “Jet-cooled
laser spectroscopy of the cyclohexoxy radical”, L. Zu, J. Liu, G. Tarczay, P. Dupré, and T. A. Miller, J. Chem. Phys. 120, 10579 (2004).
167
TD06
15 min 9:55
ANOMALOUS Λ-DOUBLING IN THE INFRARED SPECTRUM OF THE HYDROXYL RADICAL IN HELIUM NANODROPLETS
P. RASTON, T. LIANG, and G. E. DOUBERLY, Department of Chemistry, University of Georgia, Athens,
Georgia 30602, USA.
The X2 Π3/2 hydroxyl (OH) radical has been isolated in superfluid 4 He nanodroplets and probed with infrared laser depletion spectroscopy. From an analysis of the Stark spectrum of the Q(3/2) transition, the Λ-doublet splittings are determined
to be 0.198(3) cm−1 and 0.369(2) cm−1 in the ground and first excited vibrational states, respectively. These splittings are
3.6 and 7.2 times larger than their respective gas phase values. A factor of 1.6 increase in the Q(1/2) Λ-doublet splitting was
previously reported for the helium solvated X2 Π1/2 NO radical [K. von Haeften, A. Metzelthin, S. Rudolph, V. Staemmler,
and M. Havenith, Phys. Rev. Lett. 95, 215301 (2005)]. A simple model is presented that predicts the observed Λ-doublet
splittings in helium solvated OH and NO. The model assumes a small parity dependence of the rotor’s effective moment
of inertia and predicts a factor of 3.6 increase in the OH ground state (J=3/2) Λ-doubling when the Be0 and Bf0 rotational
constants differ by less than one percent.
TD07
15 min 10:12
HELIUM NANODROPLET ISOLATION SPECTROSCOPY AND AB INITIO CALCULATIONS OF HO3 -(O2 )N
CLUSTERS (N=0-4)
T. LIANG, P. RASTON, and G. E. DOUBERLY, Department of Chemistry, University of Georgia, Athens,
Georgia 30602, USA.
The HOOO hydridotrioxygen radical and its deuterated analog (DOOO) have been isolated in helium nanodroplets following the in-situ association reaction between OH and O2 . The infrared spectrum in the 3500-3700 cm−1 region reveals
bands that are assigned to the ν1 (OH stretch) fundamental and ν1 + ν6 (OH stretch plus torsion) combination band of
the trans-HOOO isomer. The helium droplet spectrum is assigned on the basis of a detailed comparison to the infrared
spectrum of HOOO produced in the gas phase [E. L. Derro, T. D. Sechler, C. Murray, and M. I. Lester, J. Chem. Phys.
128, 244313 (2008)]. Despite the characteristic low temperature and rapid cooling of helium nanodroplets, there is no
evidence for the formation of a weakly bound OH-O2 van der Waals complex, which implies the absence of a kinetically
significant barrier in the entrance channel of the reaction. There is also no spectroscopic evidence for the formation of
cis-HOOO, which is predicted by theory to be nearly isoenergetic to the trans isomer. Stark spectroscopy of the transHOOO species provides vibrationally averaged dipole moment components that qualitatively disagree with predictions
obtained from CCSD(T) computations at the equilibrium, planar geometry, indicating a floppy complex undergoing largeamplitude motion about the torsional coordinate. Under conditions that favor the introduction of multiple O2 molecules
to the droplets, bands associated with larger H/DOOO-(O2 )n clusters are observed shifted 1-10 cm−1 to the red of the
trans-H/DOOO ν1 bands. Detailed ab initio calculations are carried out for multiple isomers of cis- and trans-HO3 -O2 ,
corresponding to either hydrogen or oxygen bonded van der Waals complexes. Comparisons to theory suggest that the
structure of the HO3 -O2 complex formed in helium droplets is a hydrogen-bonded 4 A′ species consisting of a trans-HO3
core. The computed binding energy of the complex is approximately 240 cm−1 . Despite the weak interaction between
trans-HO3 and O2 , non-additive red shifts of the OH stretch frequency are observed upon successive solvation by O2 to
form the larger clusters with n>1.
Intermission
168
TD08
15 min 10:45
FOURIER TRANSFORM INFRARED SPECTROSCOPY OF CH3 OO RADICAL IN MID-INFRARED RANGE
KUO-HSIANG HSU and YUAN-PERN LEE, Department of Applied Chemistry and Institute of Molecular
Science, National Chiao Tung University, Hsinchu 30010, Taiwan and Institute of Atomic and Molecular
Sciences, Academia Sinica, Taipei 10617; MENG HUANG and TERRY A. MILLER, Laser Spectroscopy
Facility, Department of Chemistry, The Ohio State University, 120 W. 18th Avenue, Columbus, Ohio 43210.
A mid-infrared spectrum of the CH3 OO radical at room temperature has been measured by Fourier-transform infrared
spectroscopy. The CH3 OO radicals were produced by photolysis of a CH3 I/O2 mixture at 248 nm or a CH3COCH3/O2
mixture at 193 nm; the total pressure is 100 Torr and the precursor is about 1.6-2.0%. The ν2 , ν5 , ν6 , ν7 , and ν9
fundamental bands with origins at 2954.0, 1182.6, 1118.0, 910.8, and 3021.4 cm−1 have been observed, which are in good
agreement with previous low-resolution work.a Particular attention has been given to simulate the rotational structure of
the ν2 band. Sequence band structure from the methyl torsion mode ν12 was included in the simulation of this band as well
as some transitions from the precursor. The simulation shows generally good consistency with the experimental spectrum
and allows the determination of the molecule’s rotational constants.
a D.-R.
Huang, L.-K. Chu, and Y.-P. Lee J. Chem. Phys. 127, 7 (2007)
TD09
15 min
FARADAY ROTATION SPECTROSCOPY OF HO2 FROM AN ATMOSPHERIC FLOW REACTOR
11:02
BRIAN BRUMFIELD, GERARD WYSOCKI, Department of Electrical Engineering, Princeton University,
Princeton, NJ 08544; WENTING SUN, YIGUANG JU, Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544.
The hydroperoxyl radical (HO2 ) is a key reactive intermediate in the low-temperature (<1000 K) and high pressure (≥1
atm) oxidation chemistry of hydrocarbons and oxygenated fuels. Chemical kinetic models have been developed for a
number of fuels in the low-temperature and high-pressure regime, but validation of these models relies on quantitative
measurements of radical intermediates such as HO2 . In situ optical measurements of HO2 at high-pressure (≥1 atm) by
absorption spectroscopy are complicated by spectral overlap from non-radical species. Faraday rotation spectroscopy
(FRS) is a sensitive magneto-optical dispersion-based technique that can be used to selectively observe signals from
radicals while strongly suppressing signals from non-radicals,a effectively eliminating the problem of spectral overlap at
high-pressures.
Recently FRS has been used in the first direct measurements of HO2 at the exit of an atmospheric flow reactor
during the oxidation of dimethyl ether (DME). An external-cavity quantum cascade laser was used to record FRS
spectra of Q-branch transitions in the ν2 vibrational band at 7.14 µm. To describe the experimental signals a numerical
spectral model was developed using line positions and intensities provided by the HITRAN 2008 spectral database. HO2
concentrations were determined through non-linear fitting of the spectral model to the experimental spectra. In this talk the
non-linear fitting of the FRS spectra to the numerical model will be presented, and the measured temperature dependence
on the concentration will be compared to results from chemical kinetic modeling of DME oxidation.
a Litfin
et al., J. Chem. Phys.72, 6602 (1980).
169
TD10
15 min
11:19
e−X
e ELECTRONIC TRANSITION OF C6 -C10 PEROXY RADICALS
OBSERVATION OF THE A
NEAL D. KLINE And TERRY A. MILLER, Laser Spectroscopy Facility, Department of Chemistry, The Ohio
State University, 120 W. 18th Avenue, Columbus, Ohio 43210..
e−X
e electronic transition of straight chain C6 -C10 peroxy radicals and of the isooctyl peroxy radical have been
The A
observed and analyzed. These larger hydrocarbons are significant constituents of gasoline with heptane (octane rating of
0) and isooctane (2,2,4 trimethylpentane; octane rating of 100) being the two standards on which the octane rating scale
is based. Spectra were obtained by abstraction of hydrogen atoms from the hydrocarbons using chlorine atoms. The
origin and -OO stretch regions of the straight chain peroxy radicals are easily identifiable. It is relatively easy to uniquely
identify hexyl peroxy, but differentiation among the spectra of the larger straight chain peroxy radicals has proven difficult.
However, isooctyl peroxy is easily distinguished and the observation of the tertiary peroxy radical along with the primary
and/or secondary peroxy radical(s) is discussed.
TD11
15 min 11:36
STRUCTURE IN THE VISIBLE ABSORPTION BANDS OF JET-COOLED PHENYL PEROXY RADICALS
MICHAEL N. SULLIVAN, KEITH FREEL, J. PARK, M.C. LIN, and MICHAEL C. HEAVEN,
Department of Chemistry, Emory University, Atlanta, GA 30322.
The visible absorption bands of the phenyl peroxy radical in the gas phase have been investigated using cavity ringdown spectroscopy. Jet-cooling was used to reduce the spectral congestion. Structured spectra spanning the range from
17,500 - 19,000 cm−1 are reported for the first time. Analyses of these data have been guided by the results from timedependent density functional calculations. The observed spectrum was found to be dominated by the bands of the B̃ 2 A′′
← X̃ 2 A′′ transition. An analysis of the rotational contour for the origin band yielded a homogeneous linewidth of 2.2
cm−1 , corresponding to a decay rate of 4.1 x 1011 s−1 . The results provide a rationale for the lack of structure in room
temperature spectra that have been previously attributed to phenyl peroxy. They also indicate that the lower energy region
of the spectrum may show resolvable structure at room temperature. If so, this would provide a more definitive signature
for monitoring phenyl peroxy in kinetic measurements.
TD12
TERAHERTZ ROTATIONAL SPECTROSCOPY OF THE SO RADICAL
15 min
11:53
M. A. MARTIN-DRUMEL, A. CUISSET, S. ELIET, G. MOURET, F. HINDLE, Laboratoire de PhysicoChimie de l’Atmosphère, EA 4493, Université du Littoral Côte d’Opale, 59140 Dunkerque, France; O. PIRALI, Institut des Sciences Moléculaires d’Orsay, CNRS, UMR 8214, Université Paris XI, bât. 210, 91405
Orsay Cedex, France; SOLEIL Synchrotron, AILES beamline, L’orme des Merisiers, Saint-Aubin, 91192 GifSur-Yvette, France.
We have recorded pure rotational transitions of SO in the THz spectral range using synchrotron-based Fourier-Transform
(FT) FIR and continous wave (CW) THz techniques.
A FT-FIR spectrum of SO has been recorded at the AILES beamline of SOLEIL synchrotron in the spectral range 44–93
cm−1 using a resolution of 0.001 cm−1 allowing an accuracy on line position of 0.00007 cm−1 (∼ 2 MHz). A multipass
absorption discharge cell aligned to an absorption path length of 24 m has been useda . A continuous electrical discharge
(1 A / 980 V) in a flowing mixture of H2 S, He, H2 and air (respectively at pressure of 0.01, 1.15, 0.14 and 0.06 mbar)
was used to produce SO. On this spectrum, 102 transitions of SO have been identified with N = 31 to 65. Among the
observed lines, 99 are detected for the first time (22 new transitions belong to the HIFI spectral windows). Due to our
limited instrumental resolution, transitions involving N ranging from 31 to 43 show unresolved fine structure triplets.
Recently, in order to observe all fine structure components in the HIFI spectral windows, we have recorded a high resolution
CW-THz spectrum of SOb . At the time of the writing, this spectrum was under analysis.
a M.
b S.
A. Martin-Drumel et al., Rev. Sci. Instrum. 82, 113106 (2011)
Eliet et al., J. Mol. Struct. 1006, 13 (2011)
170
TE. MATRIX/CONDENSED PHASE
Chair: MARILYN JACOX, NIST, Gaithersburg, MD
TE01
INFRARED SPECTROSCOPY OF HNO AND NOH SUSPENDED IN SOLID PARAHYDROGEN
15 min 8:30
DAVID T. ANDERSON AND MAHMUT RUZI, Department of Chemistry, University of Wyoming, Laramie,
WY 82071-3838.
The only report in the literature on the infrared spectroscopy of the parent oxynitrene NOH was performed using Ar matrix
isolation spectroscopy at 10 K.a In this previous study, the NOH is synthesized by co-deposition of NO/Ar and a H2 /Ar
mixture that is passed through a microwave discharge to create H-atoms. The H-atoms recombine with NO in the Ar matrix
to produce mostly HNO, but some NOH is produced as well. In this work we irradiate NO doped parahydrogen solids at 2
K using 193 nm radiation which is known to generate H-atoms as by-products.b After the photolysis laser is stopped, we
detect growth of HNO and NOH presumably due to reactions of H-atoms with NO analogous to the previous Ar matrix
study. The higher energy NOH isomer is predicted by high-level calculations to be in a triplet ground electronic state.c
Interestingly, the infrared absorptions of NOH for the two observed vibrational modes (bend and OH stretch) display fine
structure; an intense central peak with smaller peaks spaced symmetrically to both lower and higher wavenumbers. Further,
the spacing between the peaks is the same for both vibrational modes. We believe this fine structure reflects the zero-field
splitting of the triplet ground state of NOH (magnetic dipole-dipole interaction) and our most current results and analysis
will be presented.
a G.
Maier, H. P. Reisenauer, M. De Marco, Angew. Chem. Int. Ed. 38, 108-110 (1999).
Fushitani and T. Momose, Low Temp. Phys. 29, 740-743 (2003).
c U. Bozkaya, J. M. Turney, Y. Yamaguchi, and H. F. Schaefer III, J. Chem. Phys. 136, 164303 (2012).
b M.
TE02
COLD CHEMICAL REACTIONS OF H-ATOMS AND N2 O IN SOLID PARAHYDROGEN AT 2 K
DAVID T. ANDERSON AND FREDRICK M. MUTUNGA,
Wyoming, Laramie, WY 82071-3838.
15 min 8:47
Department of Chemistry, University of
We report on the results of chemical reactions of H-atoms with N2 O in solid parahydrogen matrices investigated by rapid
scan FTIR. The reaction is initiated by the 193 nm in situ photodissociation of N2 O to produce N2 + O(1 D). We assume
the O(1 D) photoproduct reacts with the parahydrogen host to create H-atoms. What we observe is growth of cis-HNNO
right after photolysis is stopped along with a later delayed growth in trans-HNNO. We assign our peaks by comparison
with a previous Xe matrix isolation studya and recent ab initio calculationsb of the anharmonic vibrational frequencies
and isotopic shifts. We performed some experiments using the 15 N18
2 O precursor molecule. Detailed study of the reaction
kinetics indicate that at 1.8 K the cis-isomer is formed exclusively by the reaction, but then converts to the lower energy
trans-isomer with time. These results are surprising because a 40 kJ/mol barrier is predicted for the H + N2 O reaction, yet
the reaction readily proceeds even at 1.8 K. We are currently studying this reaction under a variety of conditions and the
most current results and analysis will be presented.
a S.
b K.
L. Laursen, A. E. Delia, and K. Mitchell, J. Phys. Chem. A 104, 3681-3692 (2000).
A. Petersen and J. S. Francisco, J. Chem. Phys. 134, 084308 (2011).
171
TE03
15 min 9:04
RYDBERG STATES OF Rb AND Cs ATOMS ON HELIUM NANODROPLETS: A RYDBERG-RITZ
ANALYSIS
Rydberg series of Rb and Cs atoms on the surface of helium nanodropletsa (HeN ) have been studied by resonance enhanced
multi-photon ionization spectroscopy and laser induced fluorescence spectroscopy. The recorded excitation spectrabc are
analyzed by using a Rydberg-Ritz approach. The dependence of the quantum defects on the principal quantum number
within a Rydberg series gives insight into the interaction between the alkali atom’s valence electron and the superfluid
helium droplet. For higher excited states a screening of the valence electron from the alkali atom core by the helium
droplet is observed. For lower states the strength of the screening effect decreases and the quantum defects are found
to lie closer to free atom values. In addition, the large spin-orbit (SO) constant of the Cs–HeN nP(2 Π) states allows a
detailed study of the influence of the helium droplet on the SO splitting as function of the principal quantum number.
Within the pseudo-diatomic picture the alkali-HeN system represents a diatomic molecule. The coupling of the Cs valence
electrons spin and the orbital angular momentum with the intermolecular axis, which is defined by the connection between
the droplet center and the alkali nucleus, depends on the strength of the atomic SO interaction. While the splitting of the
62 P1/2 (2 Π1/2 ) and 62 P3/2 (2 Π3/2 ) components has an atom-like character (Hund’s case (c) coupling), the SO splitting of
higher n states is lower than the atomic value (Hund’s case (a) coupling).
a C. Callegari and W. E. Ernst, Helium Droplets as Nanocryostats for Molecular Spectroscopy - from the Vacuum Ultraviolet to the Microwave Regime,
in: Handbook of High-Resolution Spectroscopy, eds. M. Quack and F. Merkt, John Wiley & Sons, Chichester, (2011)
b F. Lackner, G. Krois, M. Theisen, M. Koch, and W.E. Ernst, Phys. Chem. Chem. Phys., 13, 18781-18788 (2011)
c F. Lackner, G. Krois, and W.E. Ernst, J. Phys. Chem. Lett., 3, 1404-1408 (2012)
TE04
15 min 9:21
DYNAMICS OF CH3 F-(ortho-H2 )n CLUSTERS IN SOLID para-H2 CRYSTAL STUDIED BY PUMP AND PROBE
SPECTROSCOPY USING TWO CW-QUATUM CASCADE LASERS
H. KAWASAKI and A. MIZOGUCHI, H. KANAMORI, Department of Physics, Tokyo Institute of Technology, Tokyo, JAPAN 152-8551.
The ν 3 vibrational band of CH3 F in solid para-H2 is known to have a distinct regular series of lines corresponding to
clusters forming CH3 F-(ortho-H2 )n , with n = 0 to 12 a . By using infrared cw-QC laser spectroscopy, we found many
satellite lines around the main n-th cluster lines b and a photochromic phenomenon among those lines c . This time, we
studied the dynamics of this reversible process by pump and probe spectroscopy using two cw-QC lasers. As direct
absorption spectroscopy using a cw-QC laser provided high resolution and good signal-to-noise ratio spectrum even in
rapid frequency scanning of 1 cm−1 with the reputation rate of 500Hz, one laser was used for monitoring the spectrum
with very small radiation power, while the other was used for pumping a target peak with much higher power. Decrease of
the pumped line and increase of the others including satellite lines were monitored in real-time with an oscilloscope and a
video camera. The rate equation of three-level model including an intermediate state was successfully applied to explain
the temporal behavior of those lines. This kinetic analysis gives us entirely new information for understanding the relation
between the spectral lines and the structure of the clusters. For example, the rate constants thus determined suggests that
there is another new regular series of the lines among the satellites lines around the n=0 main line.
a K.
Yoshioka and D. T. Anderson, J. Chem. Phys. 119, 4731(2003)
R. W. McKellar, A. Mizoguchi, and H. Kanamori, J. Chem. Phys., 135, 124511 (2011)
c A. R. W. McKellar, A. Mizoguchi, and H. Kanamori, Phys. Chem. Chem. Phys. 13, 11587(2011)
b A.
172
TE05
15 min 9:38
TERAHERTZ TIME DOMAIN SPECTROSCOPY OF SIMPLE ASTROPHYSICALLY RELEVANT ICES: THE
STRUCTURE OF THE ICE
SERGIO IOPPOLO, Division of Geological and Planetary Sciences, California Institute of Technology,
Pasadena, CA 91125; MARCO A. ALLODI, BRETT A. McGUIRE, MATTHEW J. KELLEY, Division of
International astronomical facilities, in particular the Herschel Space Telescope, SOFIA and ALMA, are currently characterizing the interstellar medium (ISM) by collecting a huge amount of new THz spectral data that must be compared to
THz laboratory spectra to be interpreted. The latter, however, are largely lacking, and this severely restricts the scientific
impact of the astronomical observations. We have recently constructed a new THz time-domain spectroscopy system to
investigate the spectra of interstellar relevant ice analogs in the range between 0.3 - 7 THz. The system is coupled to a
FT-IR spectrometer to monitor the ices in the mid-IR (4000 - 500 cm−1 ).
The THz region of the electromagnetic spectrum is dominated by large amplitude motions, such as phonon modes and
intermolecular vibrations, along with high-frequency torsional motions of individual species. This talk will focus on the
laboratory investigation of the composition and structure of the bulk phases of interstellar ice analogs (i.e., H2 O, CO2 , CO,
CH3 OH, NH3 , CH4 ). Different temperatures, mixing ratios, and matrix isolation experiments will be shown. The ultimate
goal of this research project is to provide the scientific community with an extensive THz ice-database, which will allow
quantitative studies of the ISM, and guide future astronomical observations of species in the solid phase.
TE06
15 min 9:55
FIRST OBSERVATION OF A VIBRATIONAL FUNDAMENTAL OF SiC6 Si TRAPPED IN SOLID Ar
T.H. LE, C.M. L. RITTBY and W.R.M. GRAHAM, Department of Physics and Astronomy, Texas Christian
University, Fort Worth, TX 76129.
We report here the first results from a Fourier transform infrared (FTIR) and density functional theory (DFT) study on
SiC6 Si, which follows earlier investigations of the SiCn Si (n = 3, 4) chains. The new molecule has been produced by
ablating a rod made of silicon and graphite powder with a Nd:YAG laser and trapping the products in solid Ar at ∼15
K. Isotopic shift measurements on FTIR spectra produced using 13 C-enriched rods combined with DFT calculations have
resulted in the assignment of the most intense infrared active mode, ν1 (σ) = 1848.2 cm−1 of linear SiC6 Si. A new isotopic
perturbation model (IPM) has been developed to investigate the isotopic vibrational spectrum that is complicated by mode
mixing. This is part of an effort directed toward understanding the structures and bonding of silicon-carbon molecules and
may help in identifying SiC6 Si in circumstellar and interstellar environments.
173
TE07
15 min 10:12
NIR LASER RADIATION INDUCED CONFORMATIONAL CHANGES AND TUNNELING LIFETIMES OF HIGHENERGY CONFORMERS OF AMINO ACIDS IN LOW-TEMPERATURE MATRICES
GABOR BAZSO, ESZTER E. NAJBAUER, GABOR MAGYARFALVI and GYORGY TARCZAY, Laboratory of Molecular Spectroscopy, Institute of Chemistry, Eotvos University, PO Box 32, H-1518, Budapest 112,
Hungary.
We review our recent results on combined matrix isolation FT-IR and NIR laser irradiation studies on glycineab , alaninec,
and cysteined . The OH and the NH stretching overtones of the low-energy conformers of these amino acids deposited in
Ar, Kr, Xe, and N2 matrices were irradiated. At the expense of the irradiated conformer, other conformers were enriched
and new, high-energy, formerly unobserved conformers were formed in the matrices. This enabled the separation and
unambiguous assignment of the vibrational transitions of the different conformers. The main conversion paths and their
efficiencies are described qualitatively showing that there are significant differences in different matrices. It was shown
that the high-energy conformer decays in the matrix by H-atom tunneling. The lifetimes of the high-energy conformers
in different matrices were measured. Based on our results we conclude that some theoretically predicted low-energy
conformers of amino acids are likely even absent in low-energy matrices due to fast H-atom tunneling.
a G.
Bazso, G. Magyarfalvi, G. Tarczay J. Mol. Struct. 1025 (Light-Induced Processes in Cryogenic Matrices Special Issue) 33–42 (2012).
Bazso, G. Magyarfalvi, G. Tarczay J. Phys. Chem. A 116 (43) 10539–10547 (2012).
c G. Bazso, E. E. Najbauer, G. Magyarfalvi, G. Tarczay J. Phys. Chem. A in press, DOI: 10.1021/jp400196b.
d E. E. Najbauer, G. Bazso, G. Magyarfalvi, G. Tarczay in preparation.
b G.
Intermission
TE08
15 min 10:45
CHARACTERIZATION OF A 1:1 METHANOL-BENZENE COMPLEX USING MATRIX ISOLATION INFRARED
SPECTROSCOPY
JAY C. AMICANGELO, NATALIE C. ROMANO, AND GEOFFREY R. DEMAY, School of Science, Penn
State Erie, Erie, PA 16563.
Matrix isolation infrared spectroscopy was used to characterize a 1:1 complex of methanol (CH3 OH) with benzene (C6 H6 ).
Co-deposition experiments with CH3 OH and C6 H6 were performed at 17 - 20 K using nitrogen and argon as the matrix
gases. New infrared bands attributable to the CH3 OH-C6 H6 complex were observed near the O-H and C-O stretching
vibrations of CH3 OH and near the hydrogen out-of-plane bending vibration of C6 H6 . The initial identification of the new
infrared bands observed was established by performing a conentration study (1:200 to 1:2000 S:M ratios), by comparing the
co-deposition spectra with the spectra of the individual monomers, by matrix annealing experiments, and by performing
experiments using isotopically labeled methanol (CD3 OD) and benzene (C6 D6 ). Quantum chemical calculations were
also performed for the CH3 OH-C6 H6 complex using density functional theory and ab initio methods. Two stable minima
were found for the complex: one in which the CH3 OH is above the C6 H6 ring with the hydroxyl hydrogen interacting
with the π cloud of the ring (H-π complex) and the other in which the CH3 OH is in the plane of the C6 H6 ring with the
hydroxyl oxygen interacting with one of the C-H bonds of the ring (CH-O complex). Comparing the calculated shifts
of the vibrational frequencies for both complexes to the observed experimental frequency shifts, it is found that the H-π
complex is in best agreement with the experimental shifts in both magnitude and direction. Therefore, it is concluded that
the geometry of the CH3 OH-C6 H6 complex observed in the matrix isolation experiments is the H-π complex.
174
TE09
15 min 11:02
VUV PHOTOLYSIS OF NH3 : A MATRIX ISOLATION STUDY OF THE MOLECULAR INTERACTIONS BETWEEN
AMIDOGEN RADICAL AND AMMONIA MOLECULES
L. KRIM, and E. L. ZINS, Laboratoire de Dynamique, Interactions et Réactivité, LADIR, CNRS,UMR 7075,
Université Pierre et Marie Curie, 4 place Jussieu, 75252 Paris cedex 05, France.
The presence of NH3 in the interstellar medium is very promising in terms of possible exobiologically-relevant reactions.
This is the reason why numerous laboratory investigations on reactions involving NH3 were carried out in the context
of astrochemistry. Among other reactions, the photolysis of NH3 was widely investigated. IR spectroscopy in solid
phase as well as in rare-gas matrices suggested the formation of NH2 radicals. In most of these experiments, samples
containing NH3 were prepared at cryogenic temperatures and further irradiated. On the other hand, since the penetration
of the photons inside the solid ices as well as inside matrices is limited, the concentration of the photoproducts is weak,
thus hindering possible secondary reaction studies. Furthermore, in addition with ice-grain irradiations, in the interstellar
clouds, the gaseous species may be subjected to irradiation during their condensation on ice grains. In order to reproduce
this effect, instead of irradiating samples obtained by condensation of NH3 or NH3 /Ne gases at low temperatures, we
carried experiments in which irradiation was carried out during the sample deposition. Thus, the amidogen radical and
complexes between this radical and ammonia molecules were prepared and isolated in a neon matrix. The formation of
(NH2 )(NH3 ), (NH2 )(NH3 )2 and (NH2 )(NH3 )3 was clearly established thanks to the comparison between the theoretical
and the experimental vibrational frequencies. Thus, such ammonia-containing aggregates may be formed in the interstellar
clouds. These complexes, as solvated radicals, may further react with carbon- and oxygen-containing species present on
the surface of ice grains. Such reactions may be a first step toward the formation of prebiotic molecules.
TE10
HOT SPOT GENERATION IN ENERGETIC MATERIALS BY APPLYING WEAK ENERGIES
15 min
11:19
MING-WEI CHEN, SIZHU YOU, KENNETH S. SUSLICK, DANA D. DLOTT , School of Chemical Sciences, University of Illinois at Urbana-Champaign, Urbana, IL 61801.
Hot spot generation in energetic materials is an important process to initiate the exothermic chemical reaction, but the
details of the fundamental science behind this process is still less-known. Although the response of energetic materials
to low velocity impact have been heavily studied with high speed imaging, the response to the IR and acoustic is still
not known. A high-speed thermal imaging microscopy apparatus was constructed to observe hot spot generation by weak
energies (∼30 THz optical frequency or 20 kHz acoustic frequency), to develop the fundamental science needed to understand energy concentration mechanisms leading to hot spot generation. Inhomogeneous crystals with defects and polymer
binders were used in the experiments, with weak energies it is possible to detect the hot spot generation without destruction
and deflagration-to-detonation transitions. We have successfully recorded the hot spot grown in the 1,3,5-trinitroperhydro1,3,5-triazine (RDX) crystal and polymer-bonded sugar simulant by applying Far-IR radiation (∼30 THz) and acoustic
sonication (20 kHz) respectively, and proceeded preliminary analysis to investigate the mechanism.
TE11
THERMAL DECOMPOSITION MECHANISM OF BUTYRALDEHYDE
15 min
11:36
COURTNEY D. HATTEN, BRIAN WARNER, EMILY WRIGHT, KEVIN KASKEY, LAURA R. McCUNN,
Department of Chemistry, Marshall University, Huntington, WV 25755.
The thermal decomposition of butyraldehyde, CH3 CH2 CH2 C(O)H, has been studied in a resistively heated SiC tubular reactor. Products of pyrolysis were identified via matrix-isolation FTIR spectroscopy and photoionization mass spectrometry
in separate experiments. Carbon monoxide, ethene, acetylene, water and ethylketene were among the products detected. To
unravel the mechanism of decomposition, pyrolysis of a partially deuterated sample of butyraldehyde was studied. Also,
the concentration of butyraldehyde in the carrier gas was varied in experiments to determine the presence of bimolecular
reactions. The results of these experiments can be compared to the dissociation pathways observed in similar aldehydes
and are relevant to the processing of biomass, foods, and tobacco.
175
TE12
5 min 11:53
THE PECULIARITIES OF THE NMR SPIN-LATTICE RELAXATION IN PROTON EXCHANGED LINBO3
IGOR VERTEGEL, Institute of Physics NAS of Ukraine, Prospect Nauki 46, 03680 Kiev, Ukraine;
EUGENY CHESNOKOV, Institute of Physics NAS of Ukraine, Prospect Nauki 46, 03680 Kiev, Ukraine;
ALEXANDER OVCHARENKO, Institute of Physics NAS of Ukraine, Prospect Nauki 46, 03680 Kiev,
Ukraine; and IVAN VERTEGEL, The Faculty of Mechanics and Mathematics, National Taras Shevchenko
University of Kiev, Ukraine.
The temperature dependence of the spin-lattice relaxation time T1 of Li7 nuclei in the temperature range (170-430 K) was
investigated in LiNbO3 polycrystalline samples: the clean and annealed ones in a hydrogen environment at temperature
around 1000◦ C. The anomaly in the temperature dependence of T1 was found in range 300-340 K for both pure and
annealed crystals. The reduction of the time T1 in the annealed lithium niobate crystal is caused by the creation of point
defects (F+ or F-centers), with the dominant F-centers contribution. An increase in the activation energy in the annealed
crystal can be explained by the following. It is known for the pure lithium niobate that an oscillation of lithium occurs in a
symmetrical potential consisting of three wells. Formation of the oxygen vacancies in the annealed crystals is accompanied
with extrinsic protons occupation of the vacancies. It leads to the symmetry violation and causes an i ncrease of the
activation barrier.
176
TF. MINI-SYMPOSIUM: SPECTROSCOPY TESTS OF FUNDAMENTAL
PHYSICS
Chair: WIM UBACHS, Vrije Universiteit, Amsterdam, The Netherlands
TF01
AN OVERVIEW OF PNC RELATED STUDIES INVOLVING HEAVY POLAR MOLECULES
15 min 1:30
AZ 85287.
Parity non-conservation studies (PNC) has given added impetus for both experimental and theoretical determination of the
properties of heavy polar molecules. An overview of the current experimental approaches used by various groups in an
attempt to the determine the electron electric dipole moment (eEDM), de , and the anapole moment of nuclei will presented.
The status of the characterization of the various molecules proposed as venues in PNC will be summarized.
TF02
15 min 1:47
ThF+ AS A CANDIDATE FOR eEDM MEASUREMENTS
MICHAEL C. HEAVEN, JOSHUA H. BARTLETT, Department of Chemistry, Emory University, Atlanta, GA
30322.
The low-lying 3 ∆1 state of ThF+ has advantageous properties for studies of the electron electric dipole moment. Calculations indicate that internal fields as high as 90 GV/cm can be generated, and there is just one isotope of ThF with significant
natural abundance. Previous experiments show two low-lying electronic states of ThF+ spaced by 315 cm−1 (JCP 136,
104305 (2012)). These are 1 Σ and 3 ∆1 , but the ordering is still in question. Experiments are in progress to determine the
electronic angular momentum of the ground state.
Laser excitation spectra for ThF+ have been recorded for transitions in the 19300-21100 cm−1 range. For eEDM studies
it is technically more convenient to work with lower energy transitions. Survey spectra covering the range 15000-19000
cm−1 are currently being recorded. Results from these measurements will be presented and their relevance to possible
eEDM studies will be discussed.
177
TF03
15 min 2:04
THE MOLECULAR FRAME ELECTRIC DIPOLE MOMENT AND HYPERFINE INTERACTIONS IN HAFNIUM
FLUORIDE, HfF
ANH LE AND TIMOTHY C. STEIMLE, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ 85287; LEONID SKRIPNIKOV AND ANATOLY V. TITOV, Petersburg Nuclear Physics
Institute, Gatchina, 188300, Russia and Quantum Mechanics Division, St. Petersburg State University, St.
Petersburg 198904, Russia.
The identification of HfF+ as a possible candidate for a de measurement has stimulated new interest in the spectroscopy
of both HfF+ a, b, c and neutral HfF a, d . Studies of the neutral are relevant because photoionization schemes can be used
to produce the cations. More importantly, computational methodologies used to predict the electronic wavefunction of
HfF+ can be effectively assessed by making a comparison of predicted and experimental properties of the neutral, which
are more readily determinable. The (1,0)[17.9]2.5 -X2 ∆3/2 band of hafnium monofluoride (HfF) has been recorded using
high-resolution laser-induced fluorescence spectroscopy both field-free and in the presence of a static electric field. The
field-free spectra of 177 HfF, 179 HfF, and 180 HfF were model to generate a set of fine and hyperfine parameters for the
X2 ∆3/2 (v=0) and [17.9]2.5 (v=1) states. The observed optical Stark shifts for the 180 HfF isotopologue were analyzed
to produce the molecular frame electric dipole moments of 1.66(1)D and 0.419(7)D for the X2 ∆3/2 and [17.9]2.5 states,
respectively. A two-step ab initio calculation consisting of a two-component generalized relativistic effective core potential
calculation (GRECP) followed by a restoration of the proper four-component wavefunction was performed to predict the
properties of ground state HfF.
a B.
J. Barker, I. O. Antonov, V. E. Bondybey, and M. C. Heaven, J. Chem. Phys., 134, 201102 (2011).
C. Cossel, D. N. Gresh, L. C. Sinclair, T. Coffey, L. V. Skripnikov, A. N. Petrov, N. S. Mosyagin, A. V. Titov, R. W. Field, E. R. Meyer,
E. A. Cornell and J. Ye, Chem. Phys. Lett., 546, 1 (2012).
c M. Grau, A. E. Leanhardt, H. Loh, L. C. Sinclair, R. P. Stutz, T. S. Yahn, and E. A. Cornell, J. Mol. Spectroc., 272, 32 (2012).
d H. Loh, R. P. Stutz, T. S. Yahn, H. Looser, R. W. Field, and E. A. Cornell, J. Mol. Spectroc.,276-277, 49 (2012).
b K.
TF04
15 min 2:21
A CONCEPT OF EFFECTIVE STATE OF ATOMS-IN-COMPOUNDS TO DESCRIBE PROPERTIES DETERMINED
BY THE VALENCE ELECTRON’S DENSITIES IN ATOMIC CORES
A.V. TITOV, Yu.V. LOMACHUK, L.V. SKRIPNIKOV, A.N. PETROV, N.S. MOSYAGIN a ,
A new method of circumscribing the effective electronic states of “atoms-in-compounds” to study the properties of
molecules and solids which are described by the operators heavily concentrated in atomic cores is discussed. Among
the properties are hyperfine structure, P,T-parity nonconservation effectsb , chemical shifts of X-ray emissionc and Mössbauer lines, etc. Advantage of the approach is that a good quantitative agreement of predicted and experimental data can
be attained. From computational point of view the method is based on the relativistic pseudopotential theory d and procedures of a posteriori recovery of wave functions (which are smoothed near atomic nuclei at the molecular calculation stage
with using the pseudopotential method) in the atomic cores. We report results of our recent investigations of a number of
diatomic molecules.
a SPbU
N.S.Mosyagin, A.N.Petrov D.deMille, Progr.Theor.Chem.Phys., 15, 253 (2006).
c Yu.V.Lomachuk, A.V.Titov,Preprint PNPI N 2890 (2012).
d N.S. Mosyagin, A.V. Zaitsevskii, A.V. Titov, Int. Rev. At. Mol. Phys. 1, 63 (2010).
b A.V.Titov,
178
TF05
15 min 2:38
VOLTAGE CONTROLLED GEOMETRIC PHASE ROTATION IN
208
Pb F.
19
J. E. FURNEAUX, NEIL SHAFER-RAY, J. COKER, P. M. RUPASINGHE„ Homer L. Dodge Department
of Physics and Astronomy, University of Oklahoma, Norman, OK 73019; and C. P. McRAVEN, Chemistry
Department, Brookhaven National Laboratory, Upton, NY 11973.
Many theoretical publications have investigated the impact of the geometric phase on measurements of the e-EDM. However, there has been surprisingly little quantitative comparison of these models with experiment. Here we create a quantum
beat experiment that starts with an optical pump and ends with an optical probe of 208 Pb19 F. This measurement includes
the ability to control a geometric phase variation of the molecular alignment by applying an appropriate bias voltage. These
experiments will then used to test the accuracy of our model calculations of geometric phase rotation.
TF06
15 min 2:55
MEASUREMENT OF THE ELECTRON’S ELECTRIC DIPOLE MOMENT IN THORIUM MONOXIDE
J. BARON, Harvard University; D. DEMILLE, Yale University; J. DOYLE, G. GABRIELSE, P. HESS,
N. HUTZLER, Harvard University; B. OLEARY, Yale University; C. PANDA, E. PETRIK, B. SPAUN, Harvard Universitya .
Some polar diatomic molecules have large effective internal electric fields (Eef f ∼ 1011 V /cmb ) that can be used to make
measurements of the electron’s electric dipole moment (eEDM) with unprecedented sensitivity. By performing precision
spectroscopy on the metastable H 3 ∆1 state of ThO p
in a cryogenic buffer gas beam, we have demonstrated a statistical
sensitivity to the eEDM of δde ≈ 1 × 10−28 e · cm/ T /days, which is competitive with the current experimental limit,
|de | < 1.05 × 10−27 e · cmc . The existence of a non-zero eEDM on this level would be evidence for the existence of
interactions that violate parity and time-reversal symmetries that are not included in the Standard Model. Many extensions
to the Standard Model (in particular supersymmetric theories) predict the eEDM to be very close to the current experimental
limit. We present an overview and discuss the characterization of systematic errors in this experiment.d
a ACME
COLLABORATION
R. Meyer and J. L. Bohn, Phys. Rev. A 78, 010502 (2008)
c J. Hudson, D. Kara, J. Smallman, B. Sauer, M. Tarbutt, E. Hinds, Nature 473 493 (2011)
d This work is supported by the NSF.
b E.
TF07
15 min 3:12
BROADBAND VELOCITY MODULATION SPECTROSCOPY OF MOLECULAR IONS FOR USE IN THE JILA
ELECTRON EDM EXPERIMENT
DANIEL N. GRESH, KEVIN C. COSSEL, ERIC A. CORNELL, and JUN YE, JILA, National Institute of
Standards and Technology and University of Colorado Department of Physics, University of Colorado, Boulder, Colorado 80309-0440, USA.
The JILA electron electric dipole moment (eEDM) experiment will use a low-lying, metastable 3 ∆1 state in trapped
molecular ions of HfF+ or ThF+ .a Prior to this work, the low-lying states of these molecules had been investigated by
PFI-ZEKE spectroscopy.b However, there were no detailed studies of the electronic structure. The recently developed
technique of frequency comb velocity modulation spectroscopy (VMS)c provides broad-bandwidth, high-resolution, ionsensitive spectroscopy, allowing the acquisition of 150 cm−1 of continuous spectra in 30 minutes over 1500 simultaneous
channels. By supplementing this technique with cw-laser VMS, we have investigated the electronic structure of HfF+ in
the frequency range of 9950 to 14600 cm−1 , accurately fitting and assigning 16 rovibronic transitions involving 8 different
electronic states including the X 1 Σ+ and a3 ∆1 states.d In addition, an observed 3 Π0+ state with coupling to both the X
and a states has been used in the actual eEDM experiment to coherently transfer population from the rovibronic ground
state of HfF+ to the eEDM science state. Furthermore, we report on current efforts of applying frequency comb VMS
at 700 - 900 nm to the study of ThF+ , which has a lower energy 3 ∆1 state and a greater effective electric field, and will
provide increased sensitivity for a measurement of the eEDM.
a A.
E. Leanhardt et. al., Journal of Molecular Spectroscopy 270, 1-25 (2011).
J. Barker, I. O. Antonov, M. C. Heaven, K. A. Peterson, Journal of Chemical Physics 136, 104305 (2012).
c L. C. Sinclair, K. C. Cossel, T. Coffey, J. Ye, E. A. Cornell, Physical Review Letters 107, 093002 (2011).
d K.C. Cossel et. al., Chemical Physics Letters 546, 1-11 (2012).
b B.
179
TF08
PROGRESS OF THE JILA ELECTRON EDM EXPERIMENT
15 min 3:29
HUANQIAN LOH, KEVIN C. COSSEL, MATT GRAU, DANIEL N. GRESH, KANG-KUEN NI, JUN YE,
and ERIC A. CORNELL, JILA, National Institute of Standards and Technology and University of Colorado
Department of Physics, University of Colorado, Boulder, Colorado 80309-0440, USA.
Molecules can be advantageous for the search for the electron electric dipole moment (eEDM) due to the large effective
electric field experienced by a bound, unpaired electron. Furthermore, the closely-spaced states of opposite parity make
the molecules easy to polarize in the lab frame. The JILA eEDM experiment currently uses HfF+ molecules in an ion trap
to achieve long coherence times to reduce systematics.a When an electric field is applied the eEDM signal is proportional
to the shift in energy splitting between two Zeeman levels in a low-lying, metastable 3 ∆1 state. We have previously
shown efficient preparation of trapped HfF+ molecules in the rovibronic ground state, X 1 Σ+ (v = 0, J = 0).b Here, we
demonstrate coherent transfer of population from the ground state to the a3 ∆1 (v = 0, J = 1) state through an intermediate
3
Π0+ state and efficient state read-out using photodissociation. In addition, we have begun to take spectroscopy data of the
hyperfine and Zeeman structure of the eEDM science state in the presence of a rotating bias electric field and a magnetic
field.
a A.
b H.
E. Leanhardt et. al., Journal of Molecular Spectroscopy 270, 1-25 (2011).
Loh et. al., Journal of Chemical Physics 135, 154308 (2011).
TF09
15 min 3:46
HYPERFINE INTERACTION IN DIATOMICS AS A TOOL FOR SUPPRESSION OF SYSTEMICS AND VERIFICATION OF THEORETICAL VALUES FOR THE EFFECTIVE ELECTRIC FIELD ON ELECTRON FOR THE ELECTRON EDM EXPERIMENTS
A.N. PETROV, L.V. SKRIPNIKOV, N.S. MOSYAGIN, A.V. TITOV a ,
An important feature of the effective electric field (Eeff ) acting on electrons is that it cannot be obtained in an experiment
and the electronic structure calculation is required for its evaluationb. Therefore, an accuracy check must be provided by
calculating the experimentally known hyperfine constants which, similarly to Eeff , depend on the electron spin density
near heavy nuclei. As was shownc the knowledge of the Ak and A⊥ constants for molecules with dominant one-electron
s-p mixed molecular orbital contribution (Ω = 1/2) provide the most important information for the Eeff accuracy check.
Howewer, the hyperfine structure for the Ω = 1 molecules, for a good approximation, is mainly determined by only one
constant, Ak . We show, nevertheless, that perturbation of the hyperfine structure of the 3 ∆1 state of WC, HfF+ and others
molecules can be detected in an experiment giving missing information for the Eeff accuracy check.
Besides we show that the difference between g-factors for the Omega-doublet levels in diatomics with hyperfine structure
can be converged to zero for some electric fieldd . The latter is important for suppressing systematic effects and is one of
the factors which determines the sensitivity limit in the eEDM search experiments.
We show that in order to reproduce the experimental hyperfine structure of PbFe obtained with high accuracy one must
take into account the dependence of the hyperfine constants on the internuclear distance.
a SPbU
Titov, N.S. Mosyagin, A.N. Petrov, T.A. Isaev, D.P. DeMille, Progr. Theor. Chem. Phys. B 15, 253 (2006)
c M.G. Kozlov, J. Phys. B: At. Mol. Opt. Phys. 30, L607 (1997)
d A. N. Petrov, Phys. Rev. A 83, 024502 (2011)
e R. J. Mawhorter et al, Phys. Rev. A 84, 022508 (2011)
b A.V.
180
TF10
15 min 4:03
ROTATIONAL SPECTRA IN SERVICE OF PARTICLE PHYSICS — ZEEMAN & HYPERFINE EFFECTS
RICHARD J MAWHORTER, ALEXANDER L. BAUM, ZACHARY GLASSMANN, BENJAMIN GIRODAS, Dept of Physics & Astronomy, Pomona College, Claremont, CA 91711; TREVOR SEARS, Chemistry Dept, Brookhaven National Laboratory, Upton, NY 11973; NEIL E. SHAFER-RAY, Homer L.
Dodge Department of Physics and Astronomy, University of Oklahoma, Norman, OK; LUKAS ALPHEI,
JENS-UWE GRABOW, Institut für Physikalische Chemie und Elektrochemie, Gottfried-Wilhelm-LeibnizUniverstät, 30167 Hannover, Germany.
Motivated by the ongoing search for the parity violating effects originated by an electron electric dipole moment (e-EDM)
or a nuclear anapole moment,the rotational spectra of heavy atom diatomic radicals like, e.g., 2 Π1/2 PbF are studied at the
unrivalled resolution offered by supersonic-jet Fourier transform microwave spectroscopy. Obtaining accurate information
on such relativistically behaving systems wil be the key to provide a delicate test to the proposed theories in extension
to the Standard Model of Physics. Employment of an MW method to hunt down these tiny effects, easily obscured by
the linewidth inherent to other techniques, in rotational transitions is a promising approach to observe the tiny energy
difference of terms that are degenerate without parity violation. Already before an experiment sensitive to parity violation,
the exceptional resolution of the microwave time-domain technique can be exploited to provide accurate tests on the
quantum chemical predictions that are part of the calculation of the anticipated e-EDM or anapole moment sensitivity of a
given species since nuclear quadrupole and magnetic hyperfine effects in the rotational spectra are closely related.
In our current experiment, transitions can be observed with 0.2 kHz accuracy for unblended lines over a range of 2 -– 26.5
GHz. The observation of field dependent spectra (in magnetic fields up to 4 Gauss) allows for the determination of the two
body fixed g-factors, G⊥ and Gk which can then be compared with recent theoretical values. YbF provides the current
e-EDM upper limit. Although it is more sensitive to magnetic fields, the nuclear quadrupole hyperfine structure of 173 YbF
constitutes a direct probe on the electric field gradient and thus can help characterize the critical electric field at the heavy
atom nucleus. We will report on 14 GHz transitions for 3 of the less abundant even isotopologues of YbF as well as the
207
PbF analogue 171 YbF, important steps towards observing 173 YbF.
TF11
PRECISE THEORETICAL STUDY OF SPECTROSCOPIC CONSTANTS IN DIATOMICS
10 min 4:20
L.V. SKRIPNIKOV, A.N. PETROV, A.V. TITOV, N.S. MOSYAGINa ,
During the last decade a significant progress in methods of molecular spectroscopy was achieved. One of the most
important applications of these methods is a measurement of an electron electric dipole moment in diatomic molecules
and cations containing heavy elements. In order to speed up such experiments, which usually prepared for many years,
one can apply accurate ab initio quantum-chemical methods to predict different spectroscopic constants of a molecule or
cation under consideration: scheme of electronic terms, vibrational and rotation constants, hyperfine structure constants,
g-factors, lifetimes etc. In such calculations both correlation and relativistic effects should be taken into account. This
is not a trivial problem for systems containing transition elements and especially lanthanides and actinides. We report
results of our recent investigations of a number of diatomics including theoretical investigation of HfF+ b . Details of used
methods are discussed.
a SPbU
C. Cossel, D. N. Gresh, L. C. Sinclair, T. Coffey, L. V. Skripnikov, A. N. Petrov, N. S. Mosyagin, A. V. Titov, R. W. Field, E. R. Meyer, E. A.
Cornell and J. Ye, Chem. Phys. Lett., 546, 1 (2012).
b K.
Intermission
181
TF12
15 min 4:50
DETERMINATION OF THE BOLTZMANN CONSTANT BY MEANS OF DOPPLER-BROADENING THERMOMETRY ON WATER AT 1.39 µm.
L. MORETTI, A. CASTRILLO, E. FASCI, M.D. DE VIZIA, Dipartimento di Matematica e Fisica, Seconda
Università di Napoli, Caserta, Italy; G. GALZERANO, P. LAPORTA, Dipartimento di Fisica, Politecnico
di Milano and IFN-CNR, Milano, Italy; A. MERLONE, INRIM, Istituto Nazionale di Ricerca Metrologica,
Torino, Italy; and L. GIANFRANI, Dipartimento di Matematica e Fisica, Seconda Università di Napoli,
Caserta, Italy.
Based upon precision laser spectroscopy in the linear regime of interaction, Doppler broadening thermometry (DBT)
consists in retrieving the Doppler width from the highly-accurate observation of the absorption profile corresponding to a
given atomic or molecular line in a gas sample at the thermodynamic equilibrium. We report on a DBT experiment based on
a pair of offset-frequency locked extended-cavity diode lasers at 1.39 µm, to probe the 44,1 →44,0 line of the H18
2 O ν1 + ν3
band. This method allows us to perform highly-accurate and reproducible frequency scans of the probe laser around a given
center frequency. A sophisticated and extremely refined spectral analysis procedure was developed for the highly-accurate
retrieval of the Doppler width, taking into account the Dicke narrowing effect, the speed-dependence of relaxation rates,
and the partial correlation between velocity-changing and rotational-state-changing collisions. In particular, the partially
correlated speed-dependent Nelkin-Ghatak model was employed to perform the spectral analysis of 718 spectra acquired in
the pressure range between 200 and 500 Pa, at the temperature of the triple point of water, using a 97%-enriched 18 O water
sample. Doppler width retrievals allowed for a spectroscopic determination of the Boltzmann constant with a combined
(type A and type B) uncertainty of 1.9×10−5, which is the best result obtained so far by means of an optical method. Our
determination is in full agreement with the recommended CODATA value.
TF13
COMB-ASSISTED QCL DOPPLER-BROADENED THERMOMETRY IN NH3 SAMPLES
15 min 5:07
MARCO MARANGONI, Dipartimento di Fisica del Politecnico di Milano, Milano, Italy; MARIA
DOMENICA DE VIZIA, LIVIO GIANFRANI, Seconda Universita Di Napoli, Caserta, Italy; INGMAR
Ann Arbor, MI.
The thermodynamic temperature of a gaseous medium at thermodynamic equilibrium can be extracted from molecular
spectra by examining: the relative intensities of rotational structures, the relative intensity of vibrational satellites, or the
Doppler width of individual rovibrational lines. Of these methods, Doppler broadening thermometry (DBT), measuring
the Doppler width of a single, well-isolated absorption profile, represents a primary method providing the most accurate
optical determinations. DBT requires highly precise, accurate and repeatable frequency scanning of a narrow-linewidth
probe laser around a given center frequency. This requirement often calls for complicated sideband-based approaches or
frequency-locking techniques.
We describe here an elegant implementation of Doppler broadening thermometry in which a room-temperature continuouswave quantum cascade laser at 9.07 µm is coherently phase-locked to a thulium frequency comb centered at 2 µm. Repeated
tuning of the repetition-rate enables wide and highly accurate frequency scans throughout multiple rovibrational lines of
ammonia. Hence, the thermodynamic temperature is retrieved from a manifold of profiles, rather than from a single,
isolated line, taking advantage of the simple scaling law that relates Doppler width and line-center frequency. This is
realized, regardless of the complexity of the adopted lineshape model, by implementing a multiple-line fitting procedure
with some relevant physical constraints.
The precision attained for the retrieved gas temperature, even in the absence of an accurate control of the thermodynamic
conditions of the ammonia sample, is as high as 50 ppm, even from an analysis of a restricted number of spectra (∼100),
acquired at different gas pressures. This represents a particularly relevant result as compared to previous DBT based upon
Doppler-width retrievals from an isolated spectral line.
182
TF14
15 min 5:24
ULTRA-LOW PHASE NOISE, HIGH RESOLUTION SPECTROMETER USING COMB-ASSISTED QUANTUM CASCADE LASERS
MARCO MARANGONI, Dipartimento di Fisica del Politecnico di Milano, Milano, Italy; LIVIO GIANFRANI, Dipartimento di Matematica e Fisica della Seconda Universita Di Napoli, Caserta, Italy; INGMAR
Ann Arbor, MI.
In recent years, optical frequency combs have been used extensively to stabilize solid state cw lasers for high resolution
spectroscopy, enabling the acquisition of absorption profiles of a gas sample with an absolutely calibrated, repeatable and
linear frequency axis. This uniquely defined and repeatable frequency axis allows for the retrieval of highly accurate
and traceable spectroscopic parameters and the ability to obtain physical insights regarding the influence of collisional
processes on the absorption line shapes. The highly accurate frequency axis has can be used in precision spectroscopy
applications such as resolving hyperfine transitions or cavity enhanced spectroscopy for trace gas detection.
To simplify such precision spectroscopy systems in the future, the use of quantum cascade lasers (QCL) as a spectroscopic
tool is highly desired. Here we report on the precision phase locking of a 9 µm QCL to a 2 µm low-noise thulium
frequency comb. Utilizing a coherent lock with a MHz-level feedback bandwidth, we line narrow a QCL with a 1 MHz
linewidth and achieve an in-loop beatnote measurement with 70 dB S/N at 1 Hz RBW. As an application, we demonstrate
the interrogation of sub-Doppler features of ammonia spectra at 9 µm. It is expected that the system is further compatible
with line narrowing of widely tunable external cavity QCL’s, opening new measurement avenues in precision spectroscopy.
TF15
NARROW OPPOSITE-PARITY LEVEL CROSSINGS IN A DIATOMIC RADICAL
10 min 5:41
S. B. CAHN, J. AMMON, Y. GUREVICH, E. ALTUNTAS, D. DEMILLE, Yale University, Dept. of Physics,
New Haven, CT, USA; R. PAOLINO, US Coast Guard Academy, New London, CT, USA; M. G. KOZLOV,
Petersburg Nuclear Physics Institute, Gatchina, Russia.
We have measured and characterized narrow opposite-parity level crossings of the BaF radical in a molecular beam by
Zeeman tuning molecular rovibrational levels to these crossings and effecting the transfer with a static electric field pulse.
Because of the exquisite homogeneity of the magnetic field (0.1 ppm) during the application of the electric field, the
crossings were as narrow as the inverse fly-through time of the radicals through this electric field pulse. The energies,
electric dipole moments, and electric polarizabilities of the crossings confirm the predictions of molecular calculations and
establish this technique as viable for the proposed measurement of the nuclear anapole moment of the 137 Ba nucleus in the
continuing experiment, and also as a testbed for the study of two-level quantum systems.
TF16
PHOTOELECTRON SPECTROSCOPY STUDIES OF URANIUM FLUORIDE
15 min 5:53
WEI-LI LI, TIAN JIAN, GARY V. LOPEZ, AND LAI-SHENG WANG , Brown University, Chemistry
Department, 324 Brook St, Providence, RI, 02912.
The uranium fluoride anions (UF−
x , x=2 - 4) are produced by laser vaporization and investigated using photoelectron
spectroscopy at four different photon energies. An extensive vibrational progression of 620 cm−1 is observed in the
spectra of UF−
4 , indicating significant geometry change between the anion and the neutral ground states. Franck-Condon
simulation is performed to identify the vertical detachment and the 0-0 transition to get the electron affinity of the neutral
UF4 . Preliminary ab initio calculation shows that the U 5f orbitals participate in the bonding with F 2p orbitals. The UF−
3
molecule has multiple vibrational modes active upon electron detachment, yielding congested photoelectron spectra. Two
−1
vibrational progressions are observed in the UF−
and 160 cm−1 .
2 spectra at 580 cm
183
TG. MINI-SYMPOSIUM: THEORY AND SPECTROSCOPY
Chair: JOHN STANTON, The University of Texas at Austin, Austin, TX
TG01
INVITED TALK
DIABATIC VERSUS ADIABATIC CALCULATION OF TORSION-VIBRATION INTERACTIONS
30 min 1:30
JON T. HOUGEN, Sensor Science Division, NIST, Gaithersburg, MD 20899-8441, USA.
The introductory part of this talk will deal briefly with two historical topics: (i) use of the words adiabatic, nonadiabatic,
and diabatic in thermodynamics and quantum mechanics, and (ii) application of diabatic and adiabatic ideas to vibrational
energy level calculations for a pair of diatomic-molecule potential energy curves exhibiting an avoided crossing. The
main part of the talk will be devoted to recent work with Li-Hong Xu and Ron Lees on how ab initio projected frequency
calculations for small-amplitude vibrations along the large-amplitude internal rotation path in methanol can best be used to
help guide experimental assignments and fits in the IR vibrational spectrum. The three CH stretching vibrations for CH3 OH
can conveniently be represented as coefficients multiplying three different types of basis vibrations, i.e., as coefficients of:
(i) the local mode C-Hi bond displacements δri for hydrogens H1 , H2 and H3 of the methyl top, (ii) symmetrized linear
combinations of the three δri of species A1 ⊕ E in the permutation-inversion group G6 = C3v appropriate for methanol,
or (iii) symmetrized linear combinations of the three δri of species 2A1 ⊕ A2 in the permutation-inversion group G6 . In
this talk, we will focus on diabatic and adiabatic computations for the A1 ⊕ E basis vibrations of case (ii) above. We will
briefly explain how Jahn-Teller-like and Renner-Teller-like torsion-vibration interaction terms occurring in the potential
energy expression in the diabatic calculation become torsion-vibration Coriolis interaction terms occurring in the kinetic
energy expression of the adiabatic calculations, and also show how, for algebraically solvable parameter choices, the same
energy levels are obtained from either calculation. A final conclusion as to which approach is computationally superior for
the numerical data given in a quantum chemistry output file has not yet been arrived at.
TG02
15 min 2:05
AB INITIO AND MODEL-HAMILTONIAN STUDY OF THE TORSIONAL VARIATION OF THE THREE CH
STRETCHING NORMAL MODES IN METHANOL
LI-HONG XU, RONALD M. LEES, Centre for Laser, Atomic and Molecular Sciences (CLAMS), Physics
Department, University of New Brunswick, 100 Tucker Park Road, Saint John, NB, Canada E2L 4L5; JON
T. HOUGEN, Sensor Sciences Division, National Institute of Standards and Technology, Gaithersburg, MD
20899-8441.
The ν2 , ν3 and ν9 CH stretching modes of methanol in the 3µm region exhibit a significant amount of torsion-vibration
interaction, as illustrated for ν9 by the facts that: (i) the three hydrogen atoms each pass through a plane of symmetry of
the molecule twice during the course of one full internal rotation motion, once at a minimum and once at a maximum in
the three-fold potential energy curve, (ii) the H atom in the plane of symmetry is nearly motionless for the ν9 mode, and
therefore (iii) the property of remaining motionless must be transferred from one H to another six times during one full
internal rotation motion. In this talk we examine quantitatively the general phenomenon of torsion-vibration interaction
in the methyl top stretching modes in two ways. First, we present plots of normal modes produced in Gaussian projected
frequency calculations that are expressed either in terms of several sets of internal coordinates, or in terms of Cartesian
displacement vectors for the methyl hydrogen atoms. Some of these plots display a nearly three-fold sine or cosine behavior, where the sine or cosine behavior is dictated by group-theoretical symmetry arguments. Other plots display stunning
features ranging from loss of simple three-fold oscillatory pattern to cusp-like peaks or dips. Somewhat surprisingly, none
of our ab initio plots for methanol exhibit a sign change after a 2π internal rotation of the methyl top. Second, we present
a relatively simple model for the three CH stretching motions, characterized by three parameters associated with: (i) a
vibrational A/E energy difference, (ii) a Jahn-Teller-like torsion-vibration interaction term within the vibrational E state,
and (iii) a Renner-Teller-like torsion-vibration interaction term within the E state. This model gives nearly quantitative
agreement with both the regular and irregular features of the ab initio plots. The good agreement suggests that various
aspects of the physics of the model can be used to understand the quite complicated Gaussian normal mode results for
ν2 , ν3 and ν9 .
184
TG03
EXTENDING DIFFUSION MONTE CARLO TO INTERNAL COORDINATES
15 min 2:22
ANDREW S. PETIT and ANNE B. McCOY, Department of Chemistry and Biochemistry, The Ohio State
Diffusion Monte Carlo (DMC) is a powerful technique for studying the properties of molecules and clusters that undergo
large-amplitude, zero-point vibrational motions. However, the overall applicability of the method is limited by the need
to work in Cartesian coordinates and therefore have available a full-dimensional potential energy surface (PES). As a
result, the development of a reduced-dimensional DMC methodology has the potential to significantly extend the range of
problems that DMC can address by allowing the calculations to be performed in the subset of coordinates that is physically
relevant to the questions being asked, thereby eliminating the need for a full-dimensional PES.
As a first step towards this goal, we describe here an internal coordinate extension of DMC that places no constraints on the choice of internal coordinates other than requiring them all to be independent. Using H+
3 and its
isotopologues as model systems, we demonstrate that the methodology is capable of successfully describing the ground
state properties of highly fluxional molecules as well as, in conjunction with the fixed-node approximation, the ν = 1
vibrationally excited states.
The calculations of the fundamentals of H+
3 and its isotopologues provided general insights into the properties of
the nodal surfaces of vibrationally excited states. Specifically, we will demonstrate that analysis of ground state probability
distributions can point to the set of coordinates that are less strongly coupled and therefore more suitable for use as nodal
coordinates in the fixed-node approximation. In particular, we show that nodal surfaces defined in terms of the curvilinear
normal mode coordinates are reasonable for the fundamentals of H2 D+ and D2 H+ despite both molecules being highly
fluxional.
TG04
PATTERNS OF BROKEN PATTERNS
15 min 2:39
R. W. FIELD, G. B. PARK, P. B. CHANGALA, J. H. BARABAN, Department of Chemistry, Massachusetts
Spectroscopy − it is all about patterns. Some patterns look so indescribably complicated that, unlike pornography, you
do not know one when you see one. It is tempting to say that, at high vibrational excitation, interactions among normal
mode basis states are so strong and widespread that all patterns are obliterated. But this is not true. When normal mode
frequencies are in near integer multiple ratios, polyads emerge. A polyad is a robust pattern often comprising many
vibrational eigenstates. Each such pattern might span many hundreds of cm−1 , and it is inevitable that several unrelated
polyad patterns overlap. When polyads overlap, it might seem impossible to disentangle them. However, the key to
disentanglement is that polyads come in families in which successive generations are related by harmonic oscillator matrix
element selection and scaling rules. Families of polyads are described by families of scaling-based effective Hamiltonian
matrices, Heff . No matter how complex and overlapped, the polyad Heff serves as a magic decoder for picking out
the polyad pattern. Sometimes the polyad patterns are systematically broken (a meta-pattern), owing to proximity to
an isomerization barrier, as occurs in highly excited bending levels of the S1 state of HCCH, which encode the trans-cis
minimum energy isomerization path. Quantum Chemists often dismiss Heff models, precisely because they are models that
do not express the full dimensionality of the complete Hamiltonian. But an Heff explains rather than describes. Shunning
Heff s is like throwing out the baby with the bath water. Don’t do it!
185
TG05
ISOMERIZATION, PERTURBATIONS, CALCULATIONS AND THE S1 STATE OF C2 H2
15 min 2:56
J. H. BARABAN, P. B. CHANGALA, J. R. P. BERK, R. W. FIELD, Department of Chemistry, Massachusetts
Preliminary analysis of the energy region of the cis-trans isomerization transition state on the S1 surface of C2 H2 has
revealed novel patterns and surprising perturbations, including unusually large (and high-order) anharmonicities, as well
as K-staggerings of several vibrational levels. These effects complicate the analysis considerably, and require new models
and calculations to account for and predict features of the observed spectra. The Ã − X̃ spectrum of acetylene has been
studied both experimentally and theoretically for almost a century, and this cycle of unexpected phenomena eliciting
innovative responses is found throughout its history. Especially in the last ten years, progress in understanding the S1 state
rovibrational level structure and cis-trans isomerization has been accelerated by combining the information available from
both ab initio computation and spectroscopic observations. The resulting dialogue has then frequently suggested fruitful
avenues for further experiments and calculations. Current challenges and recent results in understanding the cis-trans
isomerization transition state region will be discussed in this context.
TG06
15 min 3:13
REDUCED DIMENSION ROVIBRATIONAL VARIATIONAL CALCULATIONS OF THE S1 STATE OF C2 H2
P. B. CHANGALA, J. H. BARABAN, R. W. FIELD, Department of Chemistry, Massachusetts Institute of
Technology, Cambridge, MA 02139, USA; J. F. STANTON, Institute for Theoretical Chemistry, Department of
Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712; A. J. MERER, Institute
of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan;.
The bending and torsional degrees of freedom in S1 acetylene, C2 H2 , are subject to severe vibrational resonances and
rovibrational interactions, which result in the low-energy vibrational polyad structure of these modes. As the internal
energy approaches that of the barrier to cis-trans isomerization, these energy level patterns undergo further large-scale
reorganization that cannot be satisfactorily treated by traditional models tied to local equilibrium geometries. Experimental
spectra in the region near the cis-trans transition state exhibit these complicated new patterns. In order to rationalize our
near-barrier observations and predict the detailed effects of cis-trans isomerization on the rovibrational energy structure,
we have performed reduced dimension rovibrational variational calculations of the S1 state. Our calculation uses a high
accuracy ab initio potential surface and a fully symmetrized extended-CNPI group theoretical treatment of a multivalued
internal coordinate system that is appropriate for bending and torsional large amplitude motions. We will discuss these
results and the insights they offer on understanding both large-scale features and spectroscopic details, such as tunneling
staggerings, of barrier-proximal rovibrational levels of the S1 state. We will also discuss spectral features by which barriers
can be located and characterized in general polyatomic systems.
186
TG07
15 min 3:30
LEAST SQUARES FITTING OF PERTURBED VIBRATIONAL POLYADS NEAR THE ISOMERIZATION BARRIER
IN THE S1 STATE OF C2 H2
A. J. MERER, Department of Chemistry, University of British Columbia, Vancouver, B.C., Canada V6T 1Z1
AND Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan.; J. H. BARABAN,
P. B. CHANGALA, and R. W. FIELD, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
The S1 electronic state of acetylene has recently been shown to have two potential minima, corresponding to cis- and transbent structures. The trans-bent isomer is the more stable, with the cis-bent isomer lying about 2670 cm−1 higher; the barrier
to isomerization lies roughly 5000 cm−1 above the trans zero-point level. The “isomerization coordinate” (along which
the molecule moves to get from the trans minimum to the barrier) is a combination of the ν3 (trans bending) and ν6 (cis
bending) vibrational normal coordinates, but the spectrum is very confused because the ν6 vibration interacts strongly with
the ν4 (torsion) vibration through Coriolis and Darling-Dennison resonances. Since the ν4 and ν6 fundamental frequencies
are almost equal,a the bending vibrational structure consists of polyads. At low vibrational energies the polyads where
these three vibrations are excited can be fitted by least squares almost to experimental accuracy with a simple model of
Coriolis and Darling-Dennison interactions, but at higher energies the huge x36 cross-anharmonicity, which is a symptom
that the levels are approaching the isomerization barrier, progressively destroys the polyad structure; in addition the levels
show an increasing even-odd staggering of their K-rotational structures, as predicted by group theory. It is not possible to
fit the levels near the barrier with a simple model, though some success has been achieved with extended models. Progress
with the fitting of the polyads near the barrier will be reviewed.
a A.
L. Utz, J. D. Tobiason, E. Carrasquillo M., L. J. Sanders and F. F. Crim, J. Chem. Phys. 98, 2742, 1993.
Intermission
TG08
15 min 4:00
COLLISIONAL LINE MIXING IN PARALLEL AND PERPENDICULAR BANDS OF LINEAR MOLECULES BY A
NON-MARKOVIAN APPROACH
JEANNA BULDYREVA, Institut UTINAM, UMR CNRS 6213, Université de Franche-Comté, 16 route de
Gray, 25030 Besançon cedex, France.
Reliable modeling of radiative transfer in planetary atmospheres requires accounting for the collisional line mixing
effects in the regions of closely spaced vibrotational lines as well as in the spectral wings. Because of too high CPU
cost of calculations from ab initio potential energy surfaces (if available), the relaxation matrix describing the influence
of collisions is usually built by dynamical scaling laws, such as Energy-Corrected Sudden law. Theoretical approaches
currently used for calculation of absorption near the band center are based on the impact approximation (Markovian
collisions without memory effects) and wings are modeled via introducing some empirical parameters [1,2]. Operating
with the traditional non-symmetric metric in the Liouville space, these approaches need corrections of the ECS-modeled
relaxation matrix elements ("relaxation times" and "renormalization procedure") in order to ensure the fundamental
relations of detailed balance and sum rules.We present an extension to the infrared absorption case of the previously
developed [3] for rototranslational Raman scattering spectra of linear molecules non-Markovian approach of ECS-type.
Owing to the specific choice of symmetrized metric in the Liouville space, the relaxation matrix is corrected for initial
bath-molecule correlations and satisfies non-Markovian sum rules and detailed balance. A few standard ECS parameters
determined by fitting to experimental linewidths of the isotropic Q-branch enable i) retrieval of these isolated-line
parameters for other spectroscopies (IR absorption and anisotropic Raman scattering); ii) reproducing of experimental
intensities of these spectra. Besides including vibrational angular momenta in the IR bending shapes, Coriolis effects are
also accounted for. The efficiency of the method is demonstrated on OCS-He and CO2 -CO2 spectra up to 300 and 60 atm,
respectively.
[1] F. Niro, C. Boulet, and J.-M. Hartmann, J. Quant. Spectrosc. Radiat. Transf. 88, 483 (2004).
[2] H. Tran, C. Boulet, S. Stefani, M. Snels, and G. Piccioni, J. Quant. Spectrosc. Radiat. Transf. 112, 925 (2011).
[3] J. Buldyreva and L. Bonamy, Phys. Rev. A 60, 370-376 (1999).
187
TG09
15 min 4:17
TUNNELING AND TUNNELING SWITCHING DYNAMICS IN PHENOL AND ORTHO-D-PHENOL: FTIR SPECTROSCOPY WITH SYNCHROTRON RADIATION AND THEORY
S. ALBERT, R PRENTNER, M. QUACK, PHYSICAL CHEMISTRY, ETH ZÜRICH, CH-8093 ZÜRICH,
SWITZERLAND; PH. LERCH, SWISS LIGHT SOURCE, PAUL-SCHERRER-INSTITUTE, CH-5232 VILLIGEN, SWITZERLAND.
The understanding of tunneling in chemical reactionsa is of fundamental interest. A particularly intriguing recent development is the theoretical prediction of tunneling switching in ortho-D-phenol (C6 H4 DOH) as opposed to phenol (C6 H5 OH)b
where only tunneling dominates the dynamics. For ortho-D-phenol at low energy, tunneling is completely suppressed
due to isotopic substitution, which introduces an asymmetry in the effective potential including zero point energy. This
localizes the molecular wavefunction in either the syn or the anti structure of ortho-D-phenol. At higher torsional states
of ortho-D-phenol, tunneling becomes dominant, thus switching the dynamics to a delocalized quantum wavefunction.
Therefore, we have investigated the rotationally resolved THz and IR spectra of phenol and ortho-D-phenol measured
with our FTIR setup at the Swiss Light Source (SLS)c using synchrotron radiation. We have been able to analyse the
torsional fundamentals, the first and second overtones of both isotopomers. A comparison of the spectra of phenol and
ortho-D-phenol indicates the theoretically predicted behavior of tunneling switching upon excitation of the torsional mode.
In detail, we shall discuss the splitting of the torsional fundamental, of its first and second overtones of phenol as well as
the fundamentals of syn- and anti- ortho-D-phenol and the possible tunneling switching in the torsional overtone region of
ortho-D-phenol. The results shall be also discussed in relation to the quasiadiabatic channel Reaction Path Hamiltonian
approachd. We shall also discuss the comparison with results for meta-D-phenol.
a M. Quack, Fundamental symmetries and symmetry violations in Handbook of High Resolution Spectroscopy, Vol. 1(Eds. M. Quack and F. Merkt),
Wiley, Chicester (2011), 659-722.
b S. Albert, Ph. Lerch, R. Prentner, M. Quack, Angew. Chem. Int. Ed. 2013, 52, 346-349.
c S. Albert and M. Quack, ChemPhysChem, 2007, 8, 1271-1281, S. Albert, K. Keppler Albert and M. Quack, High Resolution Fourier Transform
Infrared Spectroscopy in Handbook of High Resolution Spectroscopy, Vol. 2 (Eds. M. Quack and F. Merkt), Wiley, Chicester 2011, 965-1021, S. Albert,
K.K. Albert, Ph. Lerch and M. Quack, Faraday Discussions 2011, 150, 71-99.
d R. Prentner, M. Quack, J. Stohner and M. Willeke Faraday Discussions 2011, 150, 130-132.
TG10
15 min 4:34
ANHARMONIC VIBRATIONAL MØLLER-PLESSET PERTURBATION THEORIES USING THE DYSON EQUATION
MATTHEW R. HERMES and SO HIRATA, Department of Chemistry, University of Illinois at UrbanaChampaign, Urbana, IL 61801.
We have developed new second-order diagrammatic perturbation theories for the anharmonic vibrational structure of
molecules and solids in the Møller-Plesset partitioning of the Hamiltonian which we refer to as XVMP2. XVMP2 uses the
size-extensive vibrational self-consistent field (XVSCF) methods for the reference wave function. In lieu of calculating
the total energies of excited vibrational states, XVMP2 calculates frequencies directly using the Dyson equation for the
single-particle vibrational Green’s function and a truncated diagrammatic sum for the Dyson self-energy. This method
enables XVMP2 to predict accurate anharmonic frequencies even for methods affected by strong anharmonic resonance
without any matrix diagonalization step.
188
TG11
15 min 4:51
PERTURBATIVE CORRECTIONS TO THE CALCULATED TRANSITION FREQUENCY AND OSCILLATOR
STRENGTH OF THE HYDROGEN BONDED OH-OSCILLATOR IN THE DONOR WATER MOLECULE IN WATER
DIMER
KASPER MACKEPRANG, HENRIK G. KJAERGAARD, Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen ; TEEMU SALMI, LAURI HALONEN, Laboratory of
Physical Chemistry, Department of Chemistry, P.O. Box 55, A.I. Virtasen aukio 1, FI-00014, University of
Helsinki, Helsinki, Finland.
In order to correct for the inaccuracies of local mode calculated transition frequencies and oscillator strengths of the XH· · · Y stretch in hydrogen bonded binary complexes, perturbation theory has been applied to the water dimer. In this
model the hydrogen bonded OH-oscillator in the donor water unit has been perturbed by coupling to the six low frequency
intermolecular modes of the binary complex. The first- and second-order corrections to the energy and the first-order
correction to the wavefunction has been obtained for the ground and excited states of water dimer. The method and results
obtained using the method on the water dimer will be presented and discussed.
TG12
15 min 5:08
VIBRATIONAL CONSTANTS FOR TRIATOMIC MOLECULES FROM FOURTH-ORDER PERTURBATION THEORY
The second vibrational anharmonicity constants (yijk ) for general non-linear triatomic molecules as derived from fourthorder Rayleigh-Schrödinger perturbation theory (VPT4) are presented. The derived constants include all force field and
Coriolis terms from the Watson Hamiltonian except for the pseudopotential. The basic theory of VPT4 is discussed,
particularly with application to molecular constants, as well as the computational methods used to derive the specific
constants. Finally, the constants are analyzed in the context of model systems such as Morse and double-well potentials.
TG13
15 min 5:25
ROTATIONAL AND ROVIBRATIONAL CONSTANTS FOR TRIATOMIC MOLECULES FROM FOURTH-ORDER
PERTURBATION THEORY
Rotational and rovibrational constants including the quadratic vibration-rotation interaction constants (the “γ"s),
vibrationally-dependent quartic centrifugal distortion constants, and equilibrium hexic centrifugal distortion constants for
general non-linear triatomic molecules as derived from fourth-order Rayleigh-Schrödinger perturbation theory (VPT4) are
presented. The derived constants include all terms from the Watson Hamiltonian except for the pseudopotential. The
resulting expressions are applied to a model molecular system, and issues such as vibrational resonance are discussed.
TG14
15 min 5:42
APPLICATION OF FOURTH-ORDER VIBRATIONAL PERTURBATION THEORY TO SMALL MOLECULES
JUSTIN Z. GONG, DEVIN A. MATTHEWS, and JOHN F. STANTON, Department of Chemistry and Biochemistry, Institute for Theoretical Chemistry, The University of Texas at Austin, Austin, Texas 78712.
Fourth-order Rayleigh-Schrödinger vibrational perturbation theory (VPT4) is applied to a variety of small molecular systems, including all terms from the Watson vibrational Hamiltonian except for the pseudopotential. The results are discussed
primarily in comparison to VPT2, and the impact of Fermi and Darling-Dennison type resonances is examined. The sensitivity of the VPT4 correction to the quality of the force field is also analyzed, especially with regards to the quintic and
sextic force constants.
189
TH. MICROWAVE
Chair: GILLES ADANDE, University of Arizona, Tucson, AZ
TH01
15 min 1:30
THE SUB-MILLIMETER WAVE SPECTROSCOPY OF MONODUTERATED AMIDOGEN RADICAL (NHD)
YUTA MOTOKI, HIROYUKI OZEKI, Department of Environmental Science, Toho University, 2-2-1
Miyama, Funabashi, 274-8510, Japan; KAORI KOBAYASHI, Department of Physics, University of Toyama,
3190 Gofuku, Toyama, 930-8555, Japan.
The amidogen radical, NH2 is one of the basically significant triatomic molecules in molecular spectroscopy and interstellar
chemistry, quantum chemistry and so on. In 1990s, the NH2 radical was detected in Sgr B2.a The monoduterated species,
NHD radical, could be observed in interstellar clouds in the future. Since NHD is light molecule, the important transitions
appear in the terahertz region. However, pervious report is limited to about 500 GHz. b
In this study, the pure rotational spectrum of NHD radical in the ground state (X˜2 A′′ ) was observed in sub-millimeter
wave region by frequency modulated sub-millimeter wave spectrometer at Toho University. This radical were produced
by a DC-glow discharge through NH3 and D2 mixture at around 220K. So far, 72,6 -63,3 and 31,2 -30,3 of NHD lines were
measured. We plan to measure terahertz transitions and report its analysis.
a E.
b K.
F. Van Dishoeck, D. J. Jansen, P. Schilke, and T. G. Phillips, ApJ, 416, 183 (1993).
Kobayashi et al., J. Chem. Phys., 107, 22 (1997).
TH02
FOURIER TRANSFORM MICROWAVE SPECTRUM OF N2 -(CH2 )2 O
15 min 1:47
YOSHIYUKI KAWASHIMA, Department of Applied Chemistry, Faculty of Engineering, Kanagawa Institute
of Technology, Atsugi, Kanagawa 243-0292, JAPAN; EIZI HIROTA, The Graduate University for Advanced
Studies, Hayama, Kanagawa 240-0193, JAPAN.
We have investigated the van der Waals complexes consisting of the one from each of the two groups: (Rg, CO, N2 or
CO2 ) and (dimethyl ether, dimethyl sulfide, ethylene oxide or ethylene sulfide), by using Fourier transform microwave
spectroscopy supplemented by ab initio MO calculations, in order to understand the dynamical behavior of van der Waals
complexes and to obtain information on the potential function to internal motions in complexesa. One example of the N2
complex was included: N2 -dimethyl ether, for which we reported a preliminary resultb . In the present study we focused
attention to the N2 -EO (ethylene oxide) complex. We have detected two sets of strong-weak pairs rotational spectra for
the 15 N2 -EO, and, because the complex was a very near prolate symmetric-top molecule with the asymmetric parameter
−0.9998, have analyzed them using the asymmetric-rotor program of S-reduction, with the standard deviation of 20 kHz
or so. The spectra of 14 N2 -EO were similar, although they were split into hyperfine components due to the nuclear
quadrupole coupling of the two nitrogen atoms. The relative intensities of the four sets of the spectra were consistent with
the assignment that the four sets of the rotational spectra were due to the four eigenstates created by the exchange of the
two nitrogen atoms of the N2 and the two methylene groups of the EO. Two isomers were then expected to exist for 15 NNEO, one with 15 N in the inner and the other in the outer position, and in fact the spectra of such isomers were observed,
accompanied by one weaker set. We have observed an interesting correlation among some of the molecular parameters:
A, DJK and DK , for the two pairs of the spectra. These perturbing effects cannot be ascribed to the first-order Coriolis
interaction between the two states under consideration, but are probably caused by a combined effect of the two internal
motions: exchanges of the equivalent atoms and/or groups in, or internal rotations of, N2 and EO.
a Y.
b Y.
Kawashima, A. Sato, Y. Orita, and E. Hirota J. Phys. Chem. A 116, 1224 2012.
Kawashima, Y. Tatamitani, Y. Morita, and E. Hirota 61st International Symposium on Molecular Spectroscopy, TE10 2006.
190
TH03
THE BROADBAND ROTATIONAL SPECTRUM AND GEOMETRY OF N2 · · · ICF3
15 min 2:04
N. R. WALKER, D. HIRD, School of Chemistry, Bedson Building, Newcastle University, Newcastle-uponTyne, NE1 7RU, U.K.; A. C. LEGON, School of Chemistry, University of Bristol, Bristol, BS8 1TS, U.K..
The rotational spectra of two isotopologues of N2 · · · ICF3 have been measured between 7 and 18.5 GHz by chirped-pulse
Fourier transform microwave spectroscopy. The rotational constant, B0 , the centrifugal distortion constants, DJ and DJK ,
and the nuclear quadrupole coupling constant of 127 I are precisely determined for isotopologues containing 14 N2 and 15 N2
respectively. The complex is a symmetric top and contains a linear arrangement of C, I, N(1) and N(2) atoms. The length of
the halogen bond between N(1) and I will be presented. Experiments which exploit a Balle-Flygare FTMW spectrometer
are currently in progress to determine the nuclear quadrupole coupling constants of the 14 N nuclei.
TH04
15 min 2:21
UNEXPECTED GENERATION AND OBSERVATION OF A T-SHAPED COMPLEX OF H2 C2 · · · AgCCH
N. R. WALKER, School of Chemistry, Bedson Building, Newcastle University, Newcastle-upon-Tyne, NE1
7RU, U.K.; S. L. STEPHENS, W. MIZUKAMI, D. P. TEW AND A. C. LEGON, School of Chemistry,
University of Bristol, Bristol, BS8 1TS, U.K..
An experiment to probe species generated within a supersonically-expanding jet consisting of SF6 , Ag, C2 H2 and argon
by broadband rotational spectroscopy revealed the existence of a T-shaped complex of hitherto unknown origin. Empirical
tests revealed that this complex requires the presence of C2 H2 and Ag within the gas sample. While the intensity of the
associated transitions are enhanced by the presence of SF6 , theoretical calculations and empirical tests implied that the
identified complex is H2 C2 · · · AgCCH rather than the original target of the experiment, H2 C2 · · · AgF. This deduction is
now supported by evidence acquired through experiments exploiting 13 C-enriched isotopic samples. Transitions have been
assigned for the H2 13 C2 · · · Ag13 C13 CH isotopologue. Data acquired from each isotopologue allows determination of the
rotational constants (B0 , C0 ) and centrifugal distortion constant, ∆J . The data are consistent with a T-shaped complex
in which the Ag atom of AgCCH binds to electrons within the π-orbitals of ethyne. Preliminary determinations of bond
lengths will be presented. Experiments are in progress to measure the spectra of deuterated isotopologues.
TH05
15 min 2:38
STRUCTURES OF THE CAGE, PRISM, AND BOOK HEXAMER WATER CLUSTERS FROM MULTIPLE ISOTOPIC
SUBSTITUTION
SIMON LOBSIGER, CRISTOBAL PEREZ, DANIEL P. ZALESKI, NATHAN SEIFERT, BROOKS H.
Department of Chemistry, Bucknell University, Lewisburg, PA 17837.
The rotational spectra of the three lowest energy conformers of the water hexamer have recently been observed and assigned
using chirped-pulse Fourier-transform microwave spectroscopy.a In that study single 18 O isotopic substitution allowed
determination of oxygen framework geometries for all three clusters. Further isotopic spectra have been recorded since
then: of water samples with 18 O:16 O ratios of 3:1 and 1:3, and of weakly deuterated water. Each spectrum results from
averaging of around 10M free-induction-decays and the achieved high S/N ratio allowed assignment for each cluster of
isotopic species with practically all possible 16 O,18 O isotopic combinations, ranging from all 16 O to all 18 O species. In
addition, all 12 single deuterium species of each conformer have been assigned. This unprecedented abundance of isotopic
information, resulting in rotational constants for close to 228 different species, is combined in new determinations of the
structures of these clusters, providing a deeper insight into the properties of the underlying hydrogen bonding.
a C.
Perez, M. T. Muckle, D. P. Zaleski, N. A. Seifert, B. Temelso, G. C. Shields, Z. Kisiel, and B. H. Pate, Science 336, 897 (2012).
191
TH06
15 min 2:55
CHARACTERIZATION OF LARGE WATER CLUSTERS BY BROADBAND ROTATIONAL SPECTROSCOPY
TEMELSO, GEORGE C. SHIELDS, Dean’s Office, College of Arts and Sciences, and Department of Chemistry, Bucknell University, Lewisburg, PA 17837; STEVEN T. SHIPMAN, IAN FINNERMAN, Division of
Natural Sciences, New College of Florida, Sarasota, FL 34243.
Most theoretical water models match with experimental result reasonably well up to n=10. For clusters larger than the
decamer there is no clear consensus in the global minimum geometries, as the low-energy landscape for a given cluster size
changes considerably depending on the model applied. However, there is agreement in considering the undecamer regime
as one of the richer pure water cluster regimes, with a large number (>50) of isomers within 1 kcal/mol of the global
minimum. Using broadband chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy operating in the 2-8
GHz frequency range, seven low-energy isomers of the water undecamer have been identified in a pulsed molecular beam.
The observed water cluster structures have been identified as belonging to four families on basis to their rotational constants
according to their different oxygen atom frameworks. These families can be explained by building up the structures from
smaller water cluster subunits. Rotational spectra consistent with theoretical predictions for two isomers of (H2 O)13 and
one of (H2 O)15 have also been identified. Due to the high density of lines observed in the broadband spectrum, the
traditional method of pattern recognition using ab-initio calculations was replaced with a new approach combining highlevel ab-initio calculations with automatic fitting tools. These autofitting routines were tested on these systems and are also
briefly described.
TH07
15 min 3:12
HYDROGEN BOND NETWORK ISOMERS OF THE WATER NONAMER AND DECAMER OBSERVED BY
BROADBAND ROTATIONAL SPECTROSCOPY
TEMELSO, GEORGE C. SHIELDS, Dean’s Office, College of Arts and Sciences, and Department of Chemistry, Bucknell University, Lewisburg, PA 17837.
After our previous study of the rotational spectrum of water clusters in the 6-18 GHza region, in order to study clusters
of larger size (>8 water molecules), a chirped-pulse Fourier transform microwave spectrometer in the 2-8 GHz frequency
range has been used to obtain the broadband rotational spectra of five water nonamer isomers and four water decamer
isomers in a pulsed molecular beam. The oxygen atom framework geometries for three nonamers and two decamers have
also been unambiguously identified from isotopic labeling measurements using an H2 18 O enriched sample. Three of the
four observed water decamer show tunneling effect associated with the internal dynamics of hydrogen-bond network in a
similar fashion as the prism water hexamer. These tunneling paths are quenched upon a single incorporation of a H2 18 O
molecule in the cluster. Due the large amount of closely-spaced rotational transitions in the H2 18 O spectrum, automated
fitting tools were employed to extract the corresponding rotational spectra, which will be also briefly described.
a C.
192
TH08
15 min 3:29
STRUCTURES OF THE LOWEST ENERGY NONAMER AND DECAMER WATER CLUSTERS FROM CHIRPEDPULSE ROTATIONAL SPECTROSCOPY
CRISTOBAL PEREZ, BROOKS H. PATE, Department of Chemistry, University of Virginia, McCormick Rd.,
Charlottesville, VA 22904-4319; ZBIGNIEW KISIEL, Institute of Physics, Polish Academy of Sciences, Al.
Lotników 32/46, 02-668 Warszawa, Poland; BERHANE TEMELSO, GEORGE C. SHIELDS, Dean’s Office,
College of Arts and Sciences, and Department of Chemistry, Bucknell University, Lewisburg, PA 17837.
In the breakthrough paper reporting observation and analysis of pure rotational spectra of the hexamer, heptamer and nonamer water clusters only one nonamer species was identified.a The advances in this experiment, as described in the previous
talk, allowed identification, among others, of five different nonamer, (H2 O)9 , conformers and of four different decamer,
(H2 O)10 , conformers. Analysis of 18 O enriched spectra resulted in determination of oxygen framework geometries for
three of the water nonamers and two of the water decamers. Determination of experimental geometries proved considerably more challenging than for the lighter clusters since isotopic changes to moments of inertia are proportionally smaller,
and there are multiple instances of near-zero principal coordinates. There are also more indications of the effect of internal
motions. These problems have been overcome by careful application of rs and least-squares rm techniques in concert with
ab initio calculations so that it was possible to match the experimental and theoretical geometries unambiguously. The
precise oxygen framework geometries obtained from chirped-pulse spectroscopy for water clusters ranging in size from
the hexamer to the decamer allow, for the first time, to identify some common features of the underlying hydrogen bonding
from direct experimental evidence.
a C.
Intermission
TH09
15 min 4:00
MILLIMETER WAVE SPECTRA OF THE INTERNAL ROTATION EXCITED STATES OF (o)H2 -H2 O AND (o)H2 D2 O
K. HARADA, Y. IWASAKI, T. GIESEN, and K. TANAKA, Department of Chemistry, Faculty of Science,
Kyushu University, Hakozaki, Higashiku, Fukuoka, 812-8581 JAPAN.
H2 -H2 O is a weakly bound complex and it has a various states according to the internal rotation for both H2 and H2 O
moieties. In our previous study,a we have reported the pure rotational transitions of the (o)H2 complex in the ground H2 O
rotational state, 000 (Σ), for both H2 -H2 O and H2 -D2 O, where (o)H2 (jH2 =1) is rotating perpendicular to the intermolecular
axis to give the projection of jH2 to the axis kH2 to be zero (i.e. Σ state).
In the present study, we have observed the rotational transitions for the 000 (Π) states in the millimeter-wave region up
to 220 GHz, where the (o)H2 is rotating around the intermolecular axis to give the projection kH2 to be one (i.e. Π state).
The center of mass bond lengths derived from the observed rotational constants for 000 (Π) are longer by 5 % than those
for 000 (Σ), while force constants for the intermolecular stretching for 000 (Π) derived from centrifugal distortion constants
are smaller by 23 % than those for 000 (Σ), suggesting the Π and Σ substates have quite different structures.
The recent theoretical calculationb indicates that for 000 (Σ), (o)H2 is bound to the oxygen site of H2 O, while for the
000 (Π) state, (o)H2 to the hydrogen site of H2 O, and the 000 (Σ) state is by 14 cm−1 more stable than the 000 (Π) state.
Observed molecular constants for 000 (Σ) and (Π) are consistent with the structures given by the theoretical calculation.
We also observed the rotational spectrum in the 101 (Σ) and (Π) states, where Σ and Π correspond to the rotation of
H2 O perpendicular and parallel to the intermolecular axis and (o)H2 is calculated to be bound to the oxygen site of H2 O.
The energy difference between the 101 (Σ) and (Π) states will be discussed due to the Criolis interaction between these
substates.
a C.
J. Whitham, K. Tanaka, and K. Harada, The 56th OSU Symposium, RD08 (2001).
van der Avoid and D. J. Nesbit, J. Chem. Phys. 134, 044314 (2011).
b Ad.
193
TH10
15 min 4:17
THE PERFORMANCE OF THE THIRD GENERATION OF CP-FTMW SPECTROMETERS ILLUSTRATED BY THE
ANALYSIS OF THE WATER HEPTAMER STRUCTURE
CRISTOBAL PEREZ, DANIEL P. ZALESKI, NATHAN A. SEIFERT, SIMON LOBSIGER, BROOKS H.
Department of Chemistry, Bucknell University, Lewisburg, PA 17837; STEVEN T. SHIPMAN, Division of
Natural Sciences, New College of Florida, Sarasota, FL 34243; DAVID W. PRATT, Department of Chemistry,
The University of Vermont, Cook Physical Sciences Building, 82 University Place, Burlington, VT 05405.
The current status of the ongoing construction of a CP-FTMW spectrometer operating in the 2-18 GHz is presented.
This new design exploits advances in high-speed digital electronics to achieve unprecedented speed and sensitivity in
molecular rotational spectroscopy. Such high-speed digitizers allow deep time-domain signal averaging, making possible
to routinely acquire 10M free-induction-decays in a single experiment, decreasing the measurement time by a factor ∼10x.
The spectrometer uses high directionality microwave antennas that permit a separation large enough to place five pulsed
nozzles with no signal loss, increasing the signal by a factor of 5/3 and minimizing sample consumption with respect to
previous designs. The minimal use of traditional microwave components included in this setup make it especially wellsuited for remote internet control, which will provide access to the instrument to a broad range of chemical community. In
order to cover a wide-range of molecular systems, liquid reservoir nozzles, pulsed laser ablation sources, and pulsed electric
discharge sources are being successfully implemented. The spectrometer performance and sensitivity are demonstrated
through the measurement and analysis of the rotational spectrum of the water heptamer.
TH11
THE CYTOSINE WATER COMPLEX
10 min 4:34
A. M. DALY, S. MATA, C. BERMUDEZ, M. BERDAKIN, I. PENA, C. CABEZAS, J. L. ALONSO, Grupo
de Espectroscopía Molecular (GEM), Edificio Quifima, Laboratorios de Espectroscopía y Bioespectroscopía,
Parque Científico, Universidad de Valladolid, 47011 Valladolid, Spain.
A multi FID system has been adapted into the operation sequencea of the LA-MB-FTMW spectrometer.b Thanks
to the reached sensitivity, one monohydrate of cytosine (A = 3725.61 (26) MHz, B = 980.385 (76) MHz, C =
777.231 (46) MHz) has been detected in the supersonic expansion.
a J.
b J.
–U. Grabow, W. Stahl, H. Dreizler, Rev. Sci. Instrum. 1996, 67, 4072 – 4084.
L. Alonso, C. Pérez, M. E. Sanz, J. C. López, S. Blanco, Phys. Chem. Chem. Phys. 2009, 11, 617 – 627.
TH12
EXPERIMENTAL EVIDENCE OF LONE PAIRS - π SYSTEM INTERACTION:
TRUM OF CHLOROTRIFLUOROETHYLENE - WATER COMPLEX
10 min 4:46
THE ROTATIONAL SPEC-
L. EVANGELISTI, Q. GOU, G. FENG and W. CAMINATI, Dipartimento di Chimica "G. Ciamician"
dell’Universitá, Via Selmi 2, I-40126 Bologna, Italy.
Chemists have always been interested in labeling the interactions between the molecules, i.e. from covalent to ionic bond or
van der Waals force. Certainly the most important non-covalent bond is the hydrogen bond, also of fundamental importance
in biology. More recently also weak Hbond, sometimes in competion with halogen bonding, have been investigated
because they have assumed a fundamental importance. Here, we show the lone pairs - π interaction prevails on the latter
ones. We measured the molecular beam Fourier transform microwave spectra of five isotopologues of the 1:1 adduct of
chlorotrifluoroethylene with water. Besides the rotational constants, the quadrupole coupling constants of the chlorine
atom have been determined. Quantum chemistry calculations, at the MP2/6-311++G(d,p) level, have been carried out in
order to obtain information about the structure and relative stability of the conformers under study.
194
TH13
15 min 4:58
MICROWAVE SPECTRA AND STRUCTURE OF H2 –CuF: OVERVIEW OF THE COMPLEXES OF HYDROGEN
WITH METAL-CONTAINING DIATOMICS
G. S. GRUBBS II, DANIEL J. FROHMAN, Department of Chemistry, Wesleyan University, 52 Lawn Avenue,
Middletown, CT, 06459-0180, USA; ZHENHONG YU, Aerodyne Research, Inc. 45 Manning Road, Billerica, MA 01821; STEWART E. NOVICK, Department of Chemistry, Wesleyan University, 52 Lawn Avenue,
Middletown, CT, 06459-0180, USA (email to SEN: [email protected]).
We present here the FTMW spectra of the various isotopologues of the intermediate
strength bound complex of dihydrogen with copper fluoride.a The bond between the two
moieties is surprisingly strong, the H–H forming the cross of the T with the Cu closest to
H2 in the C2v structure. Laser ablation was used to produce both copper isotopologues
of p-H2 –CuF, o-D2 –CuF, and HD–CuF whose J = 1 − 0 transitions were observed.
Significant changes in the nuclear quadrupole coupling constants for the copper nucleus
in H2 –CuF compared to that in uncomplexed CuF suggests bonding greater than that
typical of van der Waals interactions. This talk will serve as the introduction to presentations at this meeting of other H2
metal containing diatomics.
a D.
J. Frohman, G. S. Grubbs II, Z. Yu, S. E. Novick, Inorg. Chem., 52, 816-822 (2013).
TH14
15 min 5:15
EFFECTS OF A REMOTE BINDING PARTNER ON THE ELECTRIC FIELD AND ELECTRIC FIELD GRADIENT AT
AN ATOM IN A WEAKLY BOUND TRIMER: MICROWAVE SPECTROSCOPY AND QUANTUM MECHANICAL
COMPUTATIONS ON Kr-SO3 AND Kr-SO3 -CO
REBECCA B. MACKENZIE, BROOKE A. TIMP, KENNETH R. LEOPOLD, Department of Chemistry, University of Minnesota, 207 Pleasant St., SE, Minneapolis, MN 55455; YIRONG MO, Department of Chemistry,
Western Michigan University, Kalamazoo, MI 49008.
Microwave spectra have been recorded for the C3v symmetric complexes Kr-SO3 and Kr-SO3 -CO. The Kr-S distances are
3.438(3) Å in Kr-SO3 and 3.488(6) Å in Kr-SO3 -CO. Thus, the addition of CO to Kr-SO3 increases the Kr-S distance by
0.050(9) Å. In contrast, the C-S distance in the trimer, 2.871(9) Å, is the same as that previously determined for SO3 -CO
to within the estimated uncertainties. Observed values of the 83 Kr nuclear quadrupole coupling constants provide direct
probes of the electric field gradient at the Kr nucleus. We find that, although the Kr and CO in the trimer are on opposite
sides of the SO3 and are thus not in direct contact, the addition of CO to Kr-SO3 reduces the electric field gradient at the
Kr nucleus by 18%. Calculations using the Block Localized Wavefunction decomposition method are used to understand
the physical origins of this change. While the magnitudes of both the electric field and the electric field gradient at the Kr
nucleus decrease upon addition of the CO to Kr-SO3 , the changes arise from different and rather complex combinations of
geometrical distortion, electrostatic, polarization, and electron transfer effects. For the electric field gradient, polarization
and structural change in the Kr-SO3 make the primary contributions while for the electric field itself, the change in the
electrostatic contribution has the largest effect. The calculated binding energies are additive, with that of the trimer very
nearly equal to the sum of the binding energies of Kr-SO3 and SO3 -CO.
195
TH15
15 min 5:32
MICROWAVE SPECTRUM AND STRUCTURE OF THE 2,6-DIFLUOROPYRIDINE-CO2 COMPLEX
CHRISTOPHER T. DEWBERRY, Department of Chemistry, University of Minnesota, 207 Pleasant St., SE,
Minneapolis, MN 55455; JESSICA L. MUELLER, MARK D. MARSHALL, HELEN O. LEUNG, Department of Chemistry, Amherst College, P.O. Box 5000, Amherst, MA 01002-5000; KENNETH R. LEOPOLD,
Department of Chemistry, University of Minnesota, 207 Pleasant St., SE, Minneapolis, MN 55455.
The microwave spectrum of the weakly bound complex formed from 2,6-difluoropyridine and CO2 has been obtained using
the Amherst broadband microwave spectrometer. Preliminary analysis indicates a structure in which the nitrogen of the
2,6-difluoropyridine is directed toward the carbon of the CO2 . However, unlike the related complex pyridine-CO2, which
is planar, the CO2 is rotated out of the plane of the heterocycle. The nitrogen-carbon van der Waals distance is 2.916 Å,
significantly larger than the 2.7977(64) Å value previously reported for pyridine-CO2. Ab initio calculations at the MP2/6311++G(2d,2p) level support a nitrogen bound geometry, but indicate an equilibrium structure in which the CO2 lies off
the C2 axis of the 2,6-difluoropyridine. One dimensional discrete variable representation (DVR) calculations using an ab
initio potential restricted to rotation of CO2 about the C2 axis of the difluoropyridine indicate that the complex is in the
high-barrier limit to internal rotation and that no splittings due to internal rotation will be observed in the spectrum.
TH16
15 min 5:49
OBSERVATION OF A MODERATE STRENGTH INTERACTION OF HYDROGEN WITH A COINAGE METAL
HALIDE: THE ROTATIONAL SPECTRUM AND STRUCTURE OF THE p-H2 -CuCl AND o-H2 -CuCl COMPLEXES
HERBERT M. PICKETT, DANIEL A. OBENCHAIN, G. S. GRUBBS II, and STEWART E. NOVICK, Department of Chemistry, Wesleyan University, 52 Lawn Avenue, Middletown, CT, 06459-0180, USA.
Rotational transitions of the p-H2 -CuCl and o-H2 -CuCl have been observed on a laser ablation equipped FTMW cavity
instrument. Computational studies preformed using the APFDa density functional and MP2 level of theory were used to
predict the structure of the p-H2 -CuCl. Measurements from the J=1–0 to the J=3–2 transitions were used to determine the
rotational constants, centrifugal distortion constants, and quadrupole coupling constants for multiple isotopologues of the
p-H2 -CuCl species. Similar constants, including spin-spin coupling constants, have also been determined for the o-H2 CuCl species for the J=2–1 and the J=3–2 transitions. The eQq of the copper in p-H2 -63 Cu35 Cl was found to be 52.058(2)
MHz, a change from the monomer 63 Cu35 Cl value of 16.1712(24) MHzb .
a A.
b K.
Austin, G. A. Petersson, M. J. Frisch, F. J. Dobek, G. Scalmani, and K. J. Throssell. Chem. Theor. Comp. 8 (2012) 4989.
D. Hensel, C. Styger, W. Jager, A. J. Merer, and M. C. L. Gerry, J. Chem. Phys. 99(1993) 3320.
196
TI. ASTRONOMICAL SPECIES AND PROCESSES
Chair: ERIC HERBST, University of Virginia, Charlottesville, VA
TI01
15 min 1:30
LARGE PICTURE OF THE GALACTIC CENTER STUDIED BY H+
3 : HIGH IONIZATION RATE, PREVAILING
WARM AND DIFFUSE GAS, AND NON-ROTATING EXPANDING MOLECULAR RING
TAKESHI OKA, Department of Astronomy and Astrophysics, Department of Chemistry, the Enrico Fermi
Institute, University of Chicago, Chicago, IL 60637; THOMAS R. GEBALLE, Gemini Observatory, Hilo,
HI 96720; NICK INDRIOLO, Department of Physics and Astronomy, Johns Hopkins University, Baltimore,
MD 21218.
Following our initial studies of the diffuse interstellar medium in the Central Molecular Zone (CMZ) of the Galactic center
(GC) toward two remarkable sightlines—one 140 pc to the West of Sgr A* near Sgr E, and the other 85 pc to the East of
Sgr A* near Sgr Ba —we are in the process of using newly identified bright stars with smooth continua suitable for H+
3
spectroscopy to both fill the gap between these sightlines and expand coverage to wider regions of the CMZ. So far we have
identified 43 qualified stars, of which 24 have been at least partially observed (i.e., in at least one spectral setting). The high
ionization rate (on the order of ζ ∼ 3 × 10−15 s−1 ) and the existence of warm (T ∼250 K) and diffuse (n ≤ 100 cm−3 )
gas previously reported in the GCb have also been observed in some of the new sightlines, indicating these conditions fill
a large portion of the CMZ.
The velocity profiles observed in the diffuse clouds, some of which show absorption extending ∼ 140 km s−1 , allow us
to draw a velocity-longitude diagram. The high-velocity fronts of such a diagram reveal the existence of an expanding
molecular ring (EMR) with radius of ∼ 140 pc and velocity of ∼ 140 km s−1 . This ring is similar to those previously
reportedc de but is qualitatively different in that it is not rotating, suggesting an expulsion rather than the gravitational
potential as causing the EMR. Possible relations between our observations and other high energy events will be discussed.
a T.
R. Geballe and T. Oka, ApJ, 709, L70 (2010).
Oka, T. R. Geballe, M. Goto, T. Usuda, and B. J. McCall ApJ, 632, 882 (2005).
c N. Kaifu, T. Kato, and T. Iguchi, Nature, 238, 105 (1972).
d N. Z. Scoville, ApJ, 175, L127 (1972).
e Y. Sofue, PASJ, 47, 551 (1995).
b T.
TI02
EXPLORING SHOCK CHEMISTRY IN ORION-KL WITH MID-J MOLECULAR TRANSITIONS
15 min 1:47
JULIE K. ANDERSON and LUCY M. ZIURYS, Department of Chemistry and Biochemistry, The University
of Arizona, Tucson, AZ 85719.
New receiver technology can allow us to probe high energy shock chemistry using ground-based telescopes. We have
mapped HCN (J = 8 → 7) and HCO+ (J = 8 → 7) emission across the 1′ x 1′ Orion-KL region using the ALMA Band
9 receiver at the Submillimeter Telescope of the Arizona Radio Observatory. A map of the SiO (J = 16 → 15) emission is
also currently underway. The mid-J HCN and HCO+ emission have very broad line widths that vary with position, which
suggest an association with the high velocity globules produced by the explosive outflow in this region. The emission
points to densities greater than 4x108 cm−3 in the shock material. Additionally, the central velocity of the molecular lines
changes across the nebula, eluding to interesting globular structures containing the molecular material.
197
TI03
15 min 2:04
FORMATION OF CH : SHOCK CHEMISTRY IN NGC 7027
+
JULIE K. ANDERSON, Department of Chemistry and Biochemistry, The University of Arizona, Tucson, AZ
85719; LUCY M. ZIURYS, Department of Chemistry and Biochemistry, The University of Arizona, Tucson,
AZ 85719; FABRICE HERPIN, LAB-OASU, France.
The formation of CH+ in the interstellar medium has been an enigma for the past 70 years. Emission from the species is
found in diffuse material, even though the major pathway leading to the species, C+ + H2 , is endothermic by 0.40 eV. The
barrier for this reaction can be greatly reduced if the H2 is vibrationally excited. Using the Heterodyne Instrument for the
Far Infrared (HIFI) on board the Herschel Space Observatory, we have mapped CH+ (J = 1 → 0), CH+ (J = 2 → 1),
and C+ (J = 3/2 → 1/2) across the face of the young planetary nebula, NGC 7027. Analysis of the spectra has shown
that CH+ , C+ , and vibrationally excited H2 apparently trace the same outflow in NGC 7027. Therefore CH+ in this nebula
likely forms from the activated C+ + H2 reaction. Spectral maps, temperatures, and abundances of CH+ will be presented
along with spectral maps of C+ .
TI04
15 min 2:21
WARM, DENSE GAS NEAR THE MASSIVE PROTOSTAR AFGL 2136 IRS 1 AS REVEALED BY ABSORPTION
FROM THE ν1 , ν2 , AND ν3 BANDS OF WATER
NICK INDRIOLO, DAVID A. NEUFELD, Department of Physics & Astronomy, Johns Hopkins University,
Baltimore, MD 21218; ANDREAS SEIFAHRT, Department of Astronomy and Astrophysics, University of
Chicago, Chicago, IL 60637; MATT J. RICHTER, Department of Physics, University of California Davis,
Davis, CA 95616.
We have identified absorption features due to 47 different ro-vibrational transitions of the ν1 and ν3 fundamental
and ν2 overtone bands of H2 O between 2.468 µm and 2.561 µm toward the massive protostar AFGL 2136 IRS 1, and
determined column densities in each rotational level. Analysis of the relative level populations indicates the absorption
arises in warm (T ≈ 500 K), very dense (nH > 1010 cm−3 ) gas in local thermodynamic equilibrium, with a total water
column density of N (H2 O) ≈ 1019 cm−2 . This gas must be very close to the central protostar, either in the inner
envelope or a circumstellar disk/torus. Our findings are consistent with results inferred from 4.7 µm CO observations,a
6 µm H2 O observations,b, and our own 2.5 µm HF observations.c This study represents the first extensive use of water
vapor absorption lines in the near infrared, and we examine the possibility of using such observations to derive physical
parameters in the gas surrounding other protostars.
a Mitchell,
G. F., et al. 1990, ApJ, 363, 554
A. M. S., & van Dishoeck, E. F. 2003, A&A, 403, 1003
c Indriolo, N., Neufeld, D. A., Seifahrt, A., & Richter, M. J. 2013, ApJ, 764, 188
b Boonman,
TI05
15 min 2:38
NEW RESULTS FROM A SPECTRAL-LINE SURVEY OF Sgr B2(N): INSIGHT INTO GAS-PHASE PROCESSES
A confusion-limited spectral line survey of Sgr B2(N) at 3, 2, and 1 mm (68 - 116, 130 - 172, and 210 - 280 GHz) using the
Kitt Peak 12 m and the Submillimeter Telescope (SMT) of the Arizona Radio Observatory has recently been completed.
While this data is still being analyzed, interesting new results have already been found. For example, a study of the spectra
of CH2 NH and CH3 NH2 has shown that these species, previously thought to be closely-related synthetically, vary greatly
in rotational temperature and distribution in Sgr B2(N). Thus the hypothesized grain synthesis of CH3 NH2 from CH2 NH
is improbable, and neutral-neutral reactions are the most likely source of these species. These data, as well as other results,
also provide insight into the physical structure of the Sgr B2(N) region.
198
TI06
15 min 2:55
CSO BROADBAND MOLECULAR LINE SURVEYS I: BENCHMARKING GOBASIC ANALYSIS SOFTWARE
MARY L. RADHUBER, JAMES L. SANDERS III, JACOB C. LAAS, BRIAN M. HAYS, SUSANNA L.
WIDICUS WEAVER, Department of Chemistry, Emory University, Atlanta, GA 30322; DAREK C. LIS,
Division of Physics, Mathematics, and Astronomy, California Institute of Technology, Pasadena, CA 91125.
Broadband molecular line surveys of hot cores can reveal important information about the chemistry of these interstellar
regions. Observations of a large number of sources allow trends to be determined, enabling comparison with chemical
models of star-forming regions. To this end, 25 broadband line surveys in the λ =1.3 mm band have been performed
using the Caltech Submillimeter Observatory. Each of these surveys is ∼ 60 GHz in bandwidth, has a noise level ≤30
mK, and contains thousands of spectral features. The challenge now becomes how to mine these surveys for useful
physical and chemical information in a reasonable timeline. The challenge is not only the vast amount of data, but also
the spectral complexity and high sensitivity, both of which lead to significant line blending. Simultaneous multi-molecule,
multi-component fitting programs with iterative analysis schemes are necessary to fully model the observed spectra of
these complex chemical sources. A new program, GOBASIC, has been written in the MATLAB numerical computing
environment for this purpose. This program has been benchmarked against a similar analysis program, MAGIX, using the
preliminary results from these line surveys. Significant improvements in the quality of the spectral fitting and the time
involved in analysis have been demonstrated using GOBASIC. The observations, analysis program design, and results of
benchmarking tests will be presented here. Details of the results from the line survey analyses will be presented in the next
talk.
TI07
15 min 3:12
CSO BROADBAND MOLECULAR LINE SURVEYS II: INTIAL CORRELATION ANALYSIS RESULTS FOR COMPLEX ORGANIC MOLECULES
JAMES L. SANDERS III, MARY L. RADHUBER, JACOB C. LAAS, BRIAN M. HAYS, DAREK C. LIS
and SUSANNA L. WIDICUS WEAVER, Emory University, Department of Chemistry, Atlanta, Georgia
30322.
As was presented in the previous talk, we have conducted 25 broadband line surveys of interstellar sources in the λ=1.3
mm band using the Caltech Submillimeter Observatory. Using the results from the spectral analysis of these observations,
the influence of physical environment on molecular complexity can be examined. Our broader research goal is to improve
astrochemical models to the point where accurate predictions of complex molecular inventory can be made based on the
physical and chemical environment of a given source. The CSO observations include a statistically-significant sample of
sources, cover a range of physical environments, and target selected frequency windows containing transitions from a set of
known complex organic molecules. We are now analyzing these line surveys to search for correlations between the relative
abundances of organic molecules and the physical properties of the source (i.e. temperature, density, mass, etc.), as well as
correlations between sets of molecules. Here we present the results from the initial quantitative analysis of these surveys,
as well as chemical trends that have been determiend. The implications of these results for astrochemical models will also
be discussed.
199
TI08
DETECTION AND FORMATION OF INTERSTELLAR c-C3 D2
15 min 3:29
SILVIA SPEZZANO, SANDRA BRÜNKEN, PETER SCHILKE, I. Physikalisches Institut, Universität zu
Köln, Zülpicher Str. 77, 50937 Köln, Germany; KARL M. MENTEN, Max-Planck-Institut für Radioastronomie, Auf dem Hügel 69, 53121 Bonn, Germany; PAOLA CASELLI, School of Physics and Astronomy,
University of Leeds, Leeds LS2 9JT, UK; MICHAEL C. McCARTHY, Harvard-Smithsonian Center for Astrophysics, 60 Garden St., Cambridge, MA 02138, and School of Engineering & Applied Sciences, Harvard
University, 29 Oxford St., Cambridge, MA 02138; LUCA BIZZOCCHI, Centro de Astronomia e Astrofísica,
Observatório Astronómico de Lisboa, Tapada da Ajuda, 1349-018 Lisboa, Portugal; SANDRA TREVINO,
IRAM, 18012, Granada, Spain; YURI AIKAWA, Department of Earth and Planetary Sciences, Kobe University, Kobe 657-8501, Japan; and STEPHAN SCHLEMMER, I. Physikalisches Institut, Universität zu Köln,
Zülpicher Str. 77, 50937 Köln, Germany.
Multiply deuterated molecules are unique observational probes for the earliest stages of star formation. Cyclopropenylidene, c-C3 H2 , is an ideal probe for deuterium chemistry. It is one of the most widespread molecules in our Galaxy and it
has the possibility of double deuteration. Furthermore, since c-C3 H2 is an ”early-type” molecule, it is a particular useful
tool to investigate early stages of a molecular cloud. This makes observations of its deuterated forms particularly important
to test time-dependent chemical codes which include deuteration processes. The centimeter and millimeter wavelength
spectra of doubly deuterated cyclopropenylidene have recently been measured in the laboratorya, allowing for the first
time a search for c-C3 D2 in space. We report the detection of c-C3 D2 in two starless cores, L1544 and TMC-1C. The
deuteration of this small hydrocarbon ring is analysed with a comprehensive gas-grain model, the first including doubly
deuterated species. The observed abundances of c-C3 D2 can be explained solely by gas-phase processes, supporting the
idea that c-C3 H2 is a good indicator of gas-phase deuteration.
a S.
Spezzano, F. Tamassia, S. Thorwirth, P. Thaddeus, C. A. Gottlieb, and M. C. McCarthy Astroph. J. Supp. Series 200(1), 2012.
Intermission
TI09
15 min 4:00
TERAHERTZ TIME DOMAIN SPECTROSCOPY OF COMPLEX ORGANIC MOLECULES IN ASTROPHYSICALLY
RELEVANT ICES
Pasadena, CA 91125; SERGIO IOPPOLO, Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125; MARCO A. ALLODI, MATTHEW J. KELLEY, Division of
We have constructed a new system to study the spectra of astrophysically-relevant ice analogs using THz time-domain
spectroscopy from 300 GHz - 7 THz. Here, we present our initial efforts to explore the spectra of pure ices of simple,
abundant interstellar species as well as complex organic molecules (COMs) and COM-doped ice mixtures. We will present
preliminary spectra of pure H2 O, CO2 , methanol (CH3 OH), and methyl formate (CH3 COOH) ices, as well as spectra of
these molecules embedded in a variety of other relevant interstellar analogs. Our results are discussed in the context of
astronomical observations and the possibility of probing ice compositions in the absence of a background radiation source.
200
TI10
15 min 4:17
THE ANALYSIS OF ACETONITRILE (CH3 CN) USING 3-D SUBMILLIMETER SPECTROSCOPY
JAMES P. MCMILLAN, SARAH M. FORTMAN, CHRISTOPHER F. NEESE, FRANK C. DE LUCIA, Department of Physics, The Ohio State University, Columbus, OH 43210.
We present our analysis of acetonitrile in the 550-650 GHz region using a previously reported experimental spectroscopic
approach. This method makes possible the calculation of lower state energy levels and transition strengths without the need
for spectral assignment. We produce results both in the standard catalog format (frequency, line strength and lower state
energy) as well as a point by point fit which allows the user to predict the complete spectrum at an arbitrary temperature.
This technique has been successfullya used in the analysis of astronomical data.
a S.
Fortman, J. McMillan, C. Neese, S. Randall, and A. Remijan, J. Mol. Spectrosc. 280, 11 (2012).
TI11
15 min 4:34
THE COMPLETE, TEMPERATURE RESOLVED EXPERIMENTAL SPECTRUM OF METHANOL BETWEEN 560
AND 654 GHZ
SARAH M. FORTMAN, CHRISTOPHER F. NEESE, and FRANK C. DE LUCIA, Department of Physics,
The Ohio State University, 191 W. Woodruff Ave., Columbus, OH 43210.
The complete spectrum of methanol (CH3 OH) in the 560.4–654.0 GHz spectral region has been characterized over a range
of astrophysically significant temperatures, 248–397 K. Analysis of experimental spectra recorded with absolute intensity
calibration over a slow temperature ramp provides a means for the simulation of the spectrum as a function of temperature
without a complete quantum mechanical (QM) model.a These results include contributions from vt = 3 and other higher
states that are difficult to model via QM techniques. They also contain contributions from the 13 C isotopologue in natural
abundance. These results are used to both provide catalogs in the usual line frequency, linestrength, and lower state energy
format and in a frequency point-by-point format that is particularly well suited for the characterization of blended lines.
In contrast to our earlier work on the semi-rigid species ethyl cyanide and vinyl cyanide, significant intensity difference
between these experimental values and those calculated by QM methods were found for some of the lines. Analysis of
these differences points to the difficulty of the calculation of dipole matrix elements in the context of the internal rotation
of the methanol molecule. We will compare our experimental intensities with the most recent QM model,b as well as an
earlier QM model that includes the variation of the dipole moment function with the torsional angle.c
a S.
M. Fortman, I. R. Medvedev, C. F. Neese, and F. C. De Lucia, Astrophys. J. 737, 20/1-6 (2011).
Xu, et al. J. Mol. Spectrosc. 251, 305-313 (2008).
c M. A. Mekhtiev, P. D. Godfrey, and J. T. Hougen, J. Mol. Spectrosc. 194, 171-178 (1999).
b L.-H.
201
TI12
SPECTROSCOPY OF ISOCYANIDES AND THEIR SEARCH IN INTERSTELLAR MEDIUM
15 min 4:51
Villeneuve d’Ascq Cedex, France; B. TERCERO, J. CERNICHARO, Centro de Astrobiología (CSIC-INTA).
Laboratory of Molecular Astrophysics. Department of Astrophysics. Ctra de Ajalvir,Km 4, 28850 Torrejón
de Ardoz, Madrid, Spain; and J.-C. GUILLEMIN, Sciences Chimiques de Rennes, UMR 6226 CNRS-ENSCR,
Avenue du Général Leclerc, CS 50837, 35708 Rennes Cedex 7, France.
Isocyanides are isomers of the corresponding nitriles and some have already been observed in the ISM (HNC, CH3NC,
HCCNC). There are few spectroscopic studies of these molecules. This is mainly due to the difficulty to synthesize this
kind of molecule. In addition their kinetic stability is poor, making the recording of the spectra delicate.
Following our recent work about diisocyanomethane (CNCH2 NC), the first microwave study of a bis-isocyanide derivativea , we decided to investigate the spectra of the cyano-isocyanomethane (CNCH2 CN) up to 660 GHz. These two
molecules are isomer of the more stable malonitrile (NCCH2 CN). In order to have homogeneous data set, we decided
to extend the range of the measurements of malonitrile which was studied only up to 240 GHzb .
This molecule is only 7 atoms, even if this is not detected in the ISM, the increase of sensitivity of ALMA may permit to
detect this molecule and its isocyanides derivatives. We will present also here results about ethylisocyanide, the isomer of
one of the most abundant complex organic molecule in the ISM. Its spectra was investigate up to 1THz. Its non detections
may be due to inaccurate prediction, it was studied only up to 33 GHzc .
All these molecules will be search in the IRAM 30-m line survey of Orion KL and in in the PRIMOS survey towards
TMC-1 and B1. In case of non detection, we will provide upper limits to their column density.
This work was supported by the CNES and the Action sur Projets de l’INSU, PCMI.
a Motyienko,
R.A. et al.A&A 544, (2012) A82
J. et al.J. Phys. 43, (1982) 1319
c Kruger, M. et al.Z. Naturforsch. A47, (1992) 1067
b Burie,
TI13
15 min 5:08
SUBMILLIMETERWAVE SPECTROSCOPY OF HIGHLY ASTROPHYSICAL INTEREST MOLECULE: HYDROXYACETONITRILE
Villeneuve d’Ascq Cedex, France; and J.-C. GUILLEMIN, Sciences Chimiques de Rennes, UMR 6226 CNRSENSCR, Avenue du Général Leclerc, CS 50837, 35708 Rennes Cedex 7, France.
Hydroxyacetonitrile is a simple derivative of methanol. This molecule has a strong astrophysical interest. In astrophysical environment, the formation of hydroxyacetonitrile (HOCH2 CN), has been shown to compete with aminomethanol
(NH2 CH2 OH), a glycine precursor, through the Strecker synthesisa . in addition its photochemistry leads to the formation
of formylcyanide (CHOCN), ketenimine (CH2 CNH), formaldehyde (CH2 O), hydrogen cyanide (HCN), carbon monoxyde
(CO)b . Its detection in the ISM will provide crucial hints in the formation process of complex organic molecules.
The lack of data about this molecule, only studied up to 50 GHzc , is mainly due to two reasons. First, this is not commercially available, the synthesis should be perform. Second, the most stable conformer is the gauche one. This exhibits large
amplitude motion due to the two equivalent configurations possible. Due to tunneling effect, each level is split into 0+ and
0− substates. This makes the analysis of the spectra delicate. We will report here the very first results obtained. This work
was supported by the CNES and the Action sur Projets de l’INSU, PCMI.
a Danger,
G. et al.ApJ 756, (2012) 11
G. et al.A&A 549, (2012) A93
c Cazzoli, G. et al.J. Chem. Soc., Faraday Trans. 2 69, (1973) 569
b Danger,
202
TI14
15 min 5:25
LABORATORY MEASUREMENTS AND ASTRONOMICAL OBSERVATIONS OF H2 NCO
+
HARSHAL GUPTA, Morrisroe Astrocience Laboratory, California Institute of Technology, Pasadena, CA
91125; CARL A. GOTTLIEB AND MICHAEL C. MCCARTHY, Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138.
We will discuss the evidence for protonated HNCO (H2 NCO+ ) in the centimeter- and millimeter-wave spectra of galactic
molecular sources rich in polyatomic molecules, and the prospects for extending the astronomical observations to other
sources. The astronomical observations were guided by laboratory measurements of the lowest rotational transitions in the
centimeter-wave band by Fourier transform microwave (FTM) spectroscopy of a supersonic molecular beam,a and over 15
transitions between 222 and 367 GHz in a low pressure dc discharge through H2 and HNCO.
a Lattanzi
et al., J. Phys. Chem. Lett. 3, 3420 (2012)
TI15
15 min 5:42
MILLIMETER AND SUBMILLIMETER WAVE SPECTRA OF THE HCOO CH3 ISOTOPOLOG OF METHYLFORMATE IN THE GROUND STATE AND IN THE FIRST EXCITED TORSIONAL STATE.
13
I. HAYKAL, L. MARGULÈS, T. R. HUET, R. A. MOTIYENKO, Laboratoire PhLAM, UMR8523 CNRSUniversité Lille 1, F-59655 Villeneuve d’Ascq Cedex, France; M. CARVAJAL, Unidad Asociada IEM-CSICDpto. de Física Aplicada, Universidad de Huelva, Spain; I. KLEINER, LISA, CNRS et Université Paris Est
et Paris Diderot, 61 av. Général de Gaulle, 94010, Créteil, France; J. C. GUILLEMIN, ENS de Chimie de
Rennes -CNRS -35700 Rennes, France; B. TERCERO, J. CERNICHARO, Centro de Astrobiología (CSICINTA). Ctra de Ajalvir, Km 4, 28850 Torrejón de Ardoz, Madrid, Spain.
The detection of nineteen new rotational transitions of the parent molecule of methylformate (HCOOCH3 ) in the second
lowest excited torsional mode (νt = 2) was recently reported in Orion-KLa, as well as the detection of eighty new lines
corresponding to the two 18 O isotopologs of methylformate in their ground statesb . The laboratory work on HCOO13 CH3
was continuedc. A wide spectral range from 50 to 940 GHz was recorded in Lille with the submillimeter-wave spectrometer
based on harmonic generation of a microwave synthesizer source, using a multiplication chain of solid state sources (50100 and 150-940 GHz) and a backward wave oscillator (100-150 GHz), and coupled to a 2.2 m cell. The absolute accuracy
of the line positions is better than 30 kHz up to 630 GHz and 50 kHz above. The two states (νt = 0 and 1) were fitted
together using the RAM Hamiltonian of the BELGI program and a new set of 45 parameters was accurately determined.
The fit contains 7050 lines corresponding to the ground state up to J = 78 and Ka = 34 and 1907 lines related to νt = 1
up to J = 59 and Ka = 24. The detection of new νt = 1 lines in Orion KL will be reported and discussed.
This work is supported by the French Programme National de Physico-Chimie du Milieu Interstellaire (CNRS), by CNES,
and by the Spanish Government through the grants FIS2011-28738-C02-02 and CONSOLIDER 2009-00038.
a S.
Takano, Y. Sakai, S. Kakimoto, M. Sasaki, and K. Kobayashi PASJ. 64, 89, 2012.
Tercero, et al. A& A. 538, A199, 2012.
c M. Carvajal, et al. A& A. 500, 1109, 2009.
b B.
203
TJ. INFRARED/RAMAN
Chair: BRIAN BRUMFIELD, Princeton University, Princeton, NJ
TJ01
15 min 1:30
SUB-DOPPLER RESOLUTION SPECTROSCOPY OF THE FUNDAMENTAL BAND OF HCl WITH AN OPTICAL
FREQUENCY COMB
K. IWAKUNI and M. ABE and H. SASADA, Department of Physics, Faculty of Science and Technology, Keio
University, 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
We have demonstrated wavelength modulation spectroscopy of HCl using a difference-frequency-generation (DFG) source
and an enhanced-cavity absorption cell. The frequency axis of the spectrum is calibrated by a fiber-based optical frequency
comb which is locked to a Rb clock linked with TAI. The pump and signal sources of DFG are a 1.06-µm Nd:YAG laser
and a 1.55-µm ECLD, and the idler wave is generated in a waveguide-type PPLN. The hyperfine structure caused by
the Cl nucleus with the spin 3/2 is resolved for the R(0), R(1), and R(2) transitions in the fundamental vibration band.
The hyperfine components of ∆F = +1, 0, −1, and the cross-over resonances are observed with a typical line width of
about 220 kHz, and the transition frequencies are measured with an uncertainty of less than 10 kHz. The pressure- and
power-dependences of the transition frequency and the spectral intensity of the cross-over resonances are also investigated.
TJ02
15 min 1:47
ABSOLUTE MEASUREMENTS OF NEAR-INFRARED CO2 TRANSITION FREQUENCIES AT THE kHz-LEVEL
DAVID A. LONG, GAR-WING TRUONG, JOSEPH T. HODGES, Material Measurement Laboratory, National Institute of Standards and Technology, 100 Bureau Drive, Gaithersburg, MD 20899, USA; and
CHARLES E. MILLER, Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive,
Pasadena, CA 91109, USA.
Measurements were made of Doppler broadened CO2 transitions in the (30013) ←− (00001) band near 1.6 µm using
frequency-stabilized cavity ring-down spectroscopy (FS-CRDS). These absolute measurements were directly linked to
a cesium atomic clock by the use of an octave-spanning, self-referenced optical frequency comb. Combined standard
uncertainties as low as 18 kHz were achieved for these weak transitions. A global fit was then performed which included
these measurements as well as an ensemble of absolute mid-infrared and far-infrared data. The resulting spectroscopic
parameters provide secondary frequency standards over a wide spectral region and should benefit atmospheric remote
sensing missions.
204
TJ03
15 min 2:04
ACCURATE DETERMINATION OF ROTATIONAL ENERGY LEVELS IN THE GROUND STATE OF 12 CH4
M. ABE, K. IWAKUNI, S. OKUBO and H. SASADA, Department of Physics, Faculty of Science and Technology, Keio University, Yokohama, Japan.
We have measured absolute frequencies of saturated absorption of 183 allowed and 21 forbidden transitions in the ν3 band
of 12 CH4 using an optical comb-referenced difference-frequency-generation spectrometer from 86.8 to 93.1 THz (from
2890 to 3100 cm−1 ) a , b . The pump and signal sources are a 1.06-µm Nd:YAG laser and a 1.5-µm extended-cavity laser
diode. An enhanced-cavity absorption cell increases the optical electric field and enhances the sensitivity. The typical
uncertainty is 3 kHz for the allowed transitions and 12 kHz for the forbidden transitions. Twenty combination differences
are precisely determined, and the scalar rotational and centrifugal distortion constants of the ground state are thereby
yielded as
Bs = (157 122 614.2 ± 1.5) kHz, Ds = (3 328.545 ± 0.031) kHz,
Hs = (190.90 ± 0.26) Hz, and
Ls = (−13.16 ± 0.76) mHz.
Here, Bs is the rotational constant and Ds , Hs and Ls are the scalar quartic, sextic, octic distortion constants. The relative uncertainties are considerably smaller than those obtained from global analysis c of Fourier-transform infrared spectroscopy.
a S.
Okubo, H. Nakayama, K. Iwakuni, H. Inaba and H. Sasada, Opt. Express 19, 23878 (2011).
Abe, K. Iwakuni, S. Okubo, and H. Sasada, J. Opt. Soc. Am. B (to be published).
c S. Albert, S. Bauerecker, V. Boudon, L. R. Brown, J. -P. Champion, M. Loëte, A. Nikitin, and M. Quack, Chem. Phys. 356, 131 (2009).
b M.
TJ04
10 min 2:21
IR/THZ DOUBLE RESONANCE SPECTROSCOPY IN THE PRESSURE BROADENED REGIME: A PATH TOWARDS ATMOSPHERIC GAS SENSING
S. SREE HARSHA , Aegis Technologies, 410 Jan Davis Drive, Huntsville, Alabama 35806; DANE J.
PHILLIPS, IERUS Technologies, 2904 Westcorp Blvd, Ste 210, Huntsville, AL 35805; FRANK C. DE LUCIA, Department of Physics, 191 Woodruff Ave., Ohio State University, Columbus, OH 43210 ; HENRY O.
EVERITT , Army Aviation and Missile RDE Center, Redstone Arsenal, AL 35898.
IR/THz double resonance (DR) spectroscopy is a technique which has been historically applied to study molecular collision
dynamics in the gas phase and in understanding optically pumped far infrared (THz) lasers. The high level of molecule
specific spectroscopic specificity achieved through this technique has led to the proposal of this technique as an attractive
candidate for remote sensing at atmospheric pressures. The relaxation of the stringent pump coincidence requirements due
to pressure broadening at elevated pressures gives an added advantage of providing additional pump coincidences with the
IR vibrational modes, which can be used to obtain a molecule specific enhanced DR specificity matrix. As a first step to
this approach we present analytical predictions and first experimental observation of new DR signatures of methyl chloride
in the pressure broadened regime.
205
TJ05
15 min 2:33
DETECTION OF NO AND S-NITROSOCOMPOUNDS USING MID-IR CAVITY RING-DOWN SPECTROSCOPY
VITALI STSIAPURA, VINCENT K. SHUALI, ANGELA ZIEGLER, KEVIN K. LEHMANN, Chemistry
Department, University of Virginia, Charlottesville, VA 22904; and BENJAMIN M. GASTON, Case Western
Reserve University, Cleveland, Ohio 44106.
Metabolic reactions of S-nitrosothiols have received much attention in biochemistry and medicine since Snitrosocompounds can act not only as donors of nitric oxide (NO) in an organism but can themselves be involved in
signal transduction. In the past few decades, the primary means of detecting S-nitrosocompounds in biological media has
been through chemiluminescence detection of NO, a technique that limits the sensitivity to ppb levels and is not able to
trace isotopologues of NO.
Here we present a cw-CRD instrument for detection of NO isotopologues released from S-nitrosocompounds with a sensitivity of 27 pptv of NO in 100 torr He (after averaging of ∼400 ringdowns). A mid-IR ec-QCL laser (Daylight Solutions)
is used to excite the ringdown cavity of finesse ∼10000 and probe the NO fundamental ro-vibrational band in the 5.2 - 5.3
µm range.
TJ06
15 min 2:50
DIFFERENTIAL OPTICAL DISPERSION SPECTROSCOPY FOR COMPARATIVE MOLECULAR QUANTIFICATION
MICHAL NIKODEM, BRIAN BRUMFIELD, GERARD WYSOCKI, Department of Electrical Engineering,
Princeton University, Princeton, NJ, 08544, USA.
A new spectroscopic technique that is based on molecular dispersion spectroscopya and enables new capabilities in chemical detection as compared to well-established laser absorption spectroscopy will be discussed in this paper. Differential
optical dispersion spectroscopy (DODiS) enables simultaneous measurement and comparison of two gas samples. This
is performed through simultaneous detection of molecular absorption that is additive and molecular dispersion that provides differential information about the samples. Therefore DODiS performs true optical addition/subtraction of absorption/dispersion spectra, which is a unique property not available with any conventional absorption-based techniques. The
DODiS measurement principle and proof-of-concept experiments involving comparative measurements with a well-known
reference gas mixture utilized as a real-time system calibration, as well as mitigation of unwanted spectral interference
from other molecules achieved through DODiS optical subtraction will be presented.
a G.
Wysocki and D. Weidmann, Opt. Express 18, 26123 (2010).
Intermission
TJ07
STUDY OF UTILIZATION OF AUTOMOTIVE DIESEL GLOW PLUG AS AN IR SOURCE
5 min 3:30
Glow plugs are used in commercially available Diesel engines to assist in cold weather starting. These devices are an
Infrared source that are consistent in their function and inexpensive. The operational temperature of a glow plug is in the
lower range of globar operational temperatures (1100 C) but is still potentially spectroscopically useful. This study seeks
to characterize these devices with respect to their utility as an infrared emission source. The spectral response of the glow
plug to input current variation was measured as was the temporal stability of the emission spectrum. Finally, comparisions
are made between the emission spectra of glow plugs and globars.
206
TJ08
FTIR STUDY OF COMUSTION SPECIES IN SEVERAL REGIONS OF A CANDLE FLAME
10 min 3:37
The complex chemical structure of the fuel in a candle flame, parafin, is broken down into smaller hydrocarbons in the
dark region just above the candle wick during combustion. This creates fuel-rich, fuel-lean, hydrocarbon reaction, and
combustion product regions in the flame during combustion that are spectroscopically rich, particularly in the infrared. IR
emissions were measured for each reaction region via collection optics focused into an FTIR and used to identify IR active
species present in that region and, when possible, temperature of the sampling region. The results of the measurements are
useful for combustion reaction modeling as well as for future validation of mass spectroscopy sampling systems.
TJ09
15 min 3:49
SPONTANEOUS RAMAN SCATTERING MEASUREMENTS OF NITROGEN VIBRATIONAL DISTRIBUTION
FUNCTION IN NANOSECOND PULSED DISCHARGE
A. ROETTGEN, I.V. ADAMOVICH, W.R. LEMPERT, Machael A. Chaszeyka Nonequilibrium Thermodynamics Laboratory, Dept. of Mechanical and Aerospace Engineering, The Ohio State University, Columbus,
OH 43210.
Fundamental energy storage and transfer characteristics of nanosecond pulsed, non-equilibrium discharge plasmas is an
area of continuing interest. These discharge environments have a wide range of potential applications, including plasma
assisted combustion, plasma flow control, and electrically-excited discharge laser development. Despite this potential, fundamental understanding of these plasmas remains uncertain, particularly, time-resolved energy partition among vibrational
and electronic states of nitrogen and oxygen during and after the discharge pulse.
In the present work, spontaneous Raman spectroscopy has been utilized in the study of vibrational energy loading and
relaxation of nitrogen in mixtures containing pure nitrogen and air (P=100 torr) in a pin-to-pin, nanosecond pulsed electric
discharge. A highly non-equilibrium vibrational distribution was observed for various gas mixtures and discharge pulse
characteristics. Experimental data was analyzed with the assistance of a master equation kinetic model.
TJ10
15 min 4:06
STIMULATED INFRARED EMISSION OF C2 H2 NEAR 3000 cm
−1
WITH CONTINUOUS-WAVE LASERS
MIKAEL SILTANEN, MARKUS METSÄLÄ, MARKKU VAINIO, and LAURI HALONEN, Department of
Chemistry, University of Helsinki, P.O. Box 55, FIN-00014 Helsinki, Finland.
We have constructed a sensitive experimental setup that can directly probe stimulated emission arising from ro-vibrational
transitions within the ground electronic state in gaseous C2 H2 . The setup has been used to record spectroscopic data on
both symmetric and anti-symmetric vibrational states. The symmetric states cannot be observed in standard one-photon
absorption experiments except as hot bands. We can determine the energies of the transitions near 3000 cm−1 with an
accuracy that is better than 0.005 cm−1 . In practice, the accuracy is limited by our wavemeter. The system is based on a
pump-probe setup of two narrow-line, continous-wave laser beams crossing inside a sample cell. The pump beam (around
13000 cm−1 ) excites the molecules and is frequency locked to the sample cell, which also acts as an optical resonator
greatly amplifying the pump beam. The probe beam (near 3000 cm−1 ) is provided by an optical parametric oscillator. The
intensity of the beam can vary slightly due to stimulated emission from the excited molecules as it makes a single pass
through the sample cell. The stimulated emission is detected by repeatedly switching the pump beam on and off while
measuring the intensity of the probe beam using phase-sensitive detection. Spectroscopic data are gathered by tuning the
wavelengths of the beams.
207
TJ11
15 min 4:23
CONTINUOUS WAVE STIMULATED RAMAN SPECTROSCOPY INSIDE A HOLLOW CORE PHOTONIC CRYSTAL FIBER
JOSÉ L. DOMÉNECH and MAITE CUETO, Instituto de Estructura de la Materia (IEM-CSIC), Serrano 123,
E-28006 Madrid, Spain. (email to J.L.D.: [email protected]).
Hollow-core photonic crystal fibersa (HCPCF) have raised new opportunities to study light-matter interaction. Dielectric or
metallic capillaries are intrinsically lossy, making poor light guides. In contrast, HCPCFs can guide light quite efficiently,
due to the band-gap effect produced by an array of smaller channels which surrounds a central hollow core with a few µm
diameter. The tight confinement of light inside the core, that can be filled with gases, as well as a long interaction length,
enhance multiple nonlinear phenomena, making it possible to devise new ways to do low signal level spectroscopy, as is
the case of high resolution stimulated Raman spectroscopy (SRS). A. Owyoungb demonstrated high resolution continuous
wave SRS in 1978. Shortly afterwards, seeking higher sensitivity, he developed the quasi-continuous SRS technique (a
high peak power pump laser, interacting with a low power cw probe laser). That variant remains today the best compromise
between resolution and sensitivity for gas-phase Raman spectroscopy.
In this work, we show the possibility of fully cw stimulated Raman spectroscopy, using a gas cell built around a HCPCF
to overcome the limitations posed by the weakness of the stimulated Raman effect when not using pulsed sources. The
interaction length (1.2 m), longer than that of a multiple pass refocusing cell, and the narrow diameter of the core (4.8
µm), can compensate for the much lower laser powers used in the cw set-up. The experimental complexity is considerably
reduced and the instrumental resolution is at the 10’s of MHz level, limited, with our fiber, by transit time effects. At
present, we have demonstrated the feasibility of the experiment, a sensitivity enhancement of ∼ 6000 over the single focus
regime, and a spectral resolution better than 0.005 cm−1 in the unresolved Q-branch of the ν1 component of the Fermi dyad
of CO2 at 1388 cm−1 . Other examples of rotationally resolved spectra will be shown: the Q branch of O2 at 1555 cm−1 ,
and the 2ν2 component of the Fermi dyad of CO2 at 1285 cm−1 .
a P.
St. Russell, Science 299, 358, 2003.
C. W. Patterson, R S. McDowell, Chem. Phys. Lett. 59, 156, 1978
b A.Owyoung,
TJ12
15 min 4:40
DEVELOPMENT OF AN EXTERNAL CAVITY QUANTUM CASCADE LASER SPECTROMETER FOR HIGHRESOLUTION SPECTROSCOPY OF MOLECULAR IONS
JACOB T. STEWART, BRADLEY M. GIBSON, Department of Chemistry, University of Illinois at UrbanaChampaign, Urbana, IL 61801; BENJAMIN J. McCALL, Departments of Chemistry and Astronomy, University of Illinois at Urbana-Champaign, Urbana, IL 61801.
Quantum cascade lasers (QCLs) have proven to be valuable tools for performing high-resolution infrared spectroscopy
because of their high output powers and availability throughout the mid-infrared region of the electromagnetic spectrum.
Despite their usefulness, typical QCLs can only be frequency tuned within a narrow window, requiring a specific laser
to be used for measuring a specific molecular target. Recent advances in QCL technology have improved the tuning
range of QCLs by creating lasers with broader gain profiles which can be used in an external cavity setup to produce
widely-tunable, single-mode infrared radiation. In collaboration with the Wysocki research group at Princeton, we are
developing a high-resolution infrared spectrometer based on an external cavity QCL (EC-QCL) system, which will allow
us to perform spectroscopy from ∼1120 – 1250 cm−1 . We will present details of the development of the instrument, as
well as preliminary spectroscopic results using the EC-QCL system. We will also outline future work we plan to perform
with this spectrometer, particularly high-resolution spectroscopy of molecular ions.
208
TJ13
15 min 4:57
FELION: A CRYOGENIC ION TRAP APPARATUS FOR SPECTROSCOPIC STUDIES WITH FELIX
S. BRÜNKEN, L. KLUGE, S. FANGHÄNEL, A. POTAPOV, O. ASVANY, and S. SCHLEMMER,
I. Physikalisches Institut, Universität zu Köln, 50937 Köln, Germany; J. OOMENS, B. REDLICH, Radboud
University Nijmegen, Institute for Molecules and Materials, FELIX Facility, 6525 ED Nijmegen, Netherlands;
A. STOFFELS, I. Physikalisches Institut, Universität zu Köln, 50937 Köln, Germany, and Radboud University
Nijmegen, Institute for Molecules and Materials, FELIX Facility, 6525 ED Nijmegen, Netherlands.
The combination of ion trapping techniques with sensitive action spectroscopy schemes has been developed in recent years
as a powerful tool to obtain spectra of gas-phase molecular ions from the UV to the (F)IR spectral regions.a Here we report
on the status of a specifically designed, dedicated cryogenic 22-pole ion trap apparatus (FELion), developed and built
in Cologne, Germany, and intended to be installed permanently at the "Free-Electron Lasers for Infrared eXperiments"
(FELIX) facility in Nijmegen, the Netherlands. This instrument will allow to record gas-phase IR and FIR spectra of
mass-selected, internally cold molecular ions at temperatures in the range 4 − 300 K. By the use of diverse ionization
methods, e.g. electron impact and electrospray ionization, a multitude of molecular ions can be generated and stored in the
trap, including astrophysically relevant species ranging in size from the three-atomic H+
3 up to large polycyclic aromatic
hydrocarbon (PAH) ions, but also biomolecular ions like amino acids, peptides, or nucleobases. In combination with the
powerful (F)IR radiation of the free electron lasers FELIX-1 and -2 (60 − 2500 cm−1 ) and FLAREb (6 − 100 cm−1 ) at
the FELIX facility, a variety of action spectroscopy schemes can be employed to study the ro-vibrational spectra of the
stored ions, such as IR multiphoton dissociation, (F)IR/UV double resonance spectroscopy, or the method of laser induced
reactions (LIR). In this talk we will give a detailed account of the experimental setup and present the first results obtained
with the new apparatus.
a e.g., S. Schlemmer, E. Lescop, J. von Richthofen, D. Gerlich, and M. A. Smith, J. Chem. Phys. 117, 2068 (2002); J. Oomens, B. G. Sartakov,
G. Meijer, and G. van Helden, Int. J. Mass Spectrom. 254, 1 (2006); T. R. Rizzo, J. A. Stearns, and O. V. Boyarkin, International Reviews in Physical
Chemistry 28, 481 (2009)
b FLARE: Free-electron Laser for Advanced spectroscopy and high-Resolution Experiments
TJ14
15 min 5:14
DEVELOPMENT OF A SHEATH-FLOW SUPERCRITICAL FLUID EXPANSION SOURCE FOR VAPORIZATION
OF NONVOLATILES AT MODERATE TEMPERATURES
BRADLEY M. GIBSON and JACOB T. STEWART, Department of Chemistry, University of Illinois at
Urbana-Champaign, Urbana, IL 61801; BENJAMIN J. McCALL, Departments of Chemistry and Astronomy, University of Illinois at Urbana-Champaign, Urbana, IL 61801.
Thermal vaporization followed by cooling in a supersonic expansion is an effective method for producing cold vapor
for spectroscopic analysis, and can be used even for large molecules such as pyrenea. However, for very low volatility
molecules such as fullerenes, the extreme temperatures needed can lead to incomplete internal coolingb or thermal decomposition. We have developed a supercritical fluid expansion source which allows us to vaporize non-volatile molecues, such
as fullerenes and large polycyclic aromatic hydrocarbons, at moderate initial temperatures (∼ 450 K) prior to supersonic
cooling. We will discuss the influence of various operating parameters, such as fluid composition, fluid temperature and
nozzle temperature, on the final translational and internal temperatures of test molecules volatilized with this source, as
well as discussing possible applications.
a B.
E. Brumfield, J. T. Stewart and B. J. McCall J. Chem. Phys. Lett. 3, 1985 (2012).
M. Gibson, J. T. Stewart, B. E. Brumfield and B. J. McCall, contribution FB05, presented at the 67th International Symposium on Molecular
Spectroscopy, Columbus, OH, USA, 2012.
b B.
209
TJ15
15 min 5:31
A NEW FAR-IR (THz) AND IR SPECTROMETER FOR THE STUDY OF ASTROCHEMICAL ICES
MARCO A. ALLODI, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125; SERGIO IOPPOLO, Division of Geology and Planetary Science, California Institute of Technology, Pasadena, CA 91125; BRETT A. McGUIRE, MATTHEW J. KELLEY, Division of
Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125; and GEOFFREY A. BLAKE, Division of Geology and Planetary Science, and Division of Chemistry and Chemical
Engineering, California Institute of Technology, Pasadena, CA 91125.
Far-IR (THz) spectroscopy provides a powerful technique capable of identifying solid phase molecules in the interstellar
medium (ISM). Thus, laboratory data of ices in the THz region of the electromagnetic spectrum have the potential to
support astronomical observations in the identification of complex organic molecules in the solid phase. In addition to
providing a spectral fingerprint, THz spectroscopy probes the phonon modes of a solid. As such, the absorptions of ices in
the THz region give insights into the structural dynamics of species in the solid phase.
This work will describe a new instrument capable of investigating ices in both the THz and Mid-IR. THz light is generated
via plasma filamentation and detected via electro-optic sampling. The ability to collect spectra of ices in the Mid-IR using
a commercial FTIR spectrometer allows us to compare the ices we create in the lab to the existing body of literature while
building up a database of THz spectra of ices to aid in astronomical observations.
TJ16
15 min 5:48
DEVELOPMENT AND APPLICATION OF A HIGHER RESOLUTION TERAHERTZ TIME-DOMAIN SPECTROMETER
DANIEL B. HOLLAND, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125 (email to D.B.H.: [email protected]); GEOFFREY A. BLAKE, Division of
Geological and Planetary Sciences, Division of Chemistry and Chemical Engineering, California Institute of
Technology, Pasadena, CA 91125.
We will present on our development and application of a terahertz (THz) time-domain spectrometer employing asynchronous optical sampling (ASOPS) between two Ti:Sapphire ultrafast lasers operating at a repetition rate of approximately
80MHz, and we thus demonstrate a THz frequency resolution approaching the limit of that repetition rate. This is an order
of magnitude improvement in resolution over typical THz time-domain spectrometers. The improved resolution is important for our primary effort of collecting THz spectra for far-infrared astronomy. We will report on various spectroscopic
applications including the THz rotational spectrum of water and low frequency pseudorotational modes in tetrahydrofuran.
Further, we will demonstrate the related use of the ASOPS virtual delay line in an all-optical transient thermoreflectance
experiment for quickly measuring the thermal conductivity of various semiconductor materials.
210
TK. ELECTRONIC
Chair: SCOTT REID, Marquette University, Milwaukee, WI
TK01
15 min 1:30
THE CHARACTER OF THE LONG-LIVED STATE FORMED FROM S1 OF PHENYLACETYLENE
PHILIP M. JOHNSON AND TREVOR J. SEARSa , Department of Chemistry, Stony Brook University, Stony
Brook, New York 11794.
Compared to other small aromatic molecules, phenylacetylene (PA) and benzonitrile exhibit strikingly anomalous photophysics on excitation to the S1 state. Firstly, products are formed on S1 excitation of a beam-cooled sample that seem to
live indefinitely (as defined by the flight time through the apparatus), while action spectra of their formation mirror the
rotationally-resolved absorption spectrum of the monomer. Secondly, the long lived products appear immediately during
the nsec. laser pulse rather than build up during the lifetime of the singlet level, as is seen in benzene, for example.b The
question has therefore arisen: is the long lived product of the S1 excitation the triplet state, as is assumed in all previous
work on other molecules, or is it an isomer of some sort? New pump-probe ionization mass spectroscopy experiments
have been performed to study the distribution of fragments and metastable ions produced by PA cation derived from the
neutral S1 state, and from the long-lived species. These combined with other experimental results showing weak long-lived
components in both the S1 fluorescence and pump-probe photoelectron spectra that we interpret as recurrence behavior,
definitively show the long-lived state is a triplet state of PA, not an isomer. PA with a singlet-triplet gap of 10000 cm−1 is
acting like intermediate case molecules with much smaller singlet-triplet gaps such as pyrazine and pyrimidine. Calculations point to the existence of four triplet states of PA at or below the energy of S1 providing a very large density of vibronic
states in which to distribute the energy from singlet-triplet crossing. PA T1 is calculated to be non-planar, in contrast to
what is found in benzene, possibly helping to explain the different photophysics.
Acknowledgments: We gratefully acknowledge G. V. Lopez for his contributions to some of the experimental masurements. Work at Brookhaven National Laboratory was carried out under Contract No. DE-AC02-98CH10886 with the U.S.
Department of Energy and supported by its Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences
and Biosciences.
a also:
b J.
Hofstein, H. Xu, T. J. Sears and P. M. Johnson, J. Phys. Chem. A 112, 1195-1201 (1999)
211
TK02
TWO-PROTON PHOTOTAUTOMERIZATION DYNAMICS OF 7-AZAINDOLE COMPLEXES
15 min 1:47
T. CHAKRABORTY, M. MUKHERJEE and S. KARMAKAR, Department of Physical Chemistry, Indian
Association for the cultivation of science, Calcutta 700032, India.E-mail: [email protected].
Light-induced tautomerization of 7-azaindole in doubly hydrogen-bonded dimeric complexes is one of the extensively
investigated photoisomerization processes in recent years. The reaction, in the case of homodimer, takes place with equal
ease in non-polar liquids at room temperature as well as in a cold supersonic jet expansion. A lot of studies were devoted
arguing whether the double proton transfer occurs sequentially or in a concerted manner. Over the past three decades it has
been assumed, on the basis of the observations of some low-temperature photophysical measurements, the double proton
exchange barrier of the dimer is ∼ 2kcal/mol. However, we notice that such measurements are flawed by artifact; the
apparent barrier depends on sample concentration in the solutions. The tautomerization of the isolated dimer is found
stopped at 10 K in an argon matrix, and we propose that the double proton exchange is coupled with the large amplitude
hydrogen bond vibrations. Furthermore, the process in several 1 : 1 complexes of the molecule with pyrazole and amides
displays remarkable contrasts with that of the homodimer. While the tautomerization in the former cases occurs extremely
efficiently in hydrocarbon solutions, is hindered fully in supersonic jet expansion condition.The observations also imply
that the effective barrier of phototautomerization in the 1 : 1 complexes is intimately correlated with the details of double
proton transfer mechanism. The details of our findings along with the predictions of some electronic structure calculations
will be presented in the talk.
References:
1. “Ultraviolet and infrared spectroscopy of matrix-isolated 7-azaindole dimer: Matrix effect on excited state tautomerization", M. Mukherjee, B. Bandyopadhyay and T. Chakraborty, Chem. Phys. Lett. 546, 74-79 (2012).
2. “Excited State Tautomerization of 7-Azaindole in a 1:1 Complex with δ-Valerolactam: A Comparative Study with
the Homodimer", M. Mukherjee, S. Karmakar and T. Chakraborty, J. Phys. Chem. A, 116, 9888-9896 (2012).
3. “Excited state tautomerization of 7-azaindole catalyzed by pyrazole", S. Karmakar, M. Mukherjee and T.
Chakraborty, Chem. Phys. Lett. 561-562, 46-51 (2013).
TK03
15 min 2:04
STRUCTURE DETERMINATION AND EXCITED STATE PROTON TRANSFER REACTION OF 1-NAPHTHOLAMMONIA CLUSTERS IN THE S1 STATE STUDIED BY UV-IR-UV MID-IR SPECTROSCOPY
SHUNPEI YOSHIKAWA, MITSUHIKO MIYAZAKI, WEILER MARTIN, Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8503 Japan; HARUKI
ISHIKAWA, Depertment of Chemistry, School of Science, Kitasato University, Minami-ku, Sagamihara
252-0373, Japan; MASAAKI FUJII, Chemical Resources Laboratory, Tokyo Institute of Technology, 4259
Nagatsuta-cho, Midori-ku, Yokohama 226-8503 Japan.
1-naphthol ammonia clusters have been studied long time as a benchmark system of the excited state proton transfer
(ESPT) reactions. Understanding the ESPT reaction in this system has still not been fully established. To detect the cluster
size dependence of the S1 state properties, many researcher extensively investigated such as emission spectra,a lifetime,b
solvents (ammonia) evaporation pattern.c Curiously, cluster structure that is fundamental to discuss the reaction has not
been determined for the system. Thus we applied an IR spectroscopy to the S1 states of the system to determine the cluster
structure and to discuss the minimum size inducing the ionic dissociation of the O-H bond in the S1 state. IR spectra
were recorded not only the O-H and N-H stretching region (3 µm) but also the skeletal vibrational region (5.5-10 µm).
Though O-H and N-H stretching vibrations do not provide useful structural information due to the broadness, the skeletal
vibrations hold the sharpness even in the S1 states. Changes in the skeletal vibrations due to the ammonia solvation, e.g.
C-O stretching and C-O-H bending, will be discussed based on a comparison with theoretical calculations.
a O.
Cheshnovsky and S. Leutwylar, J. Chem. Phys. 1, 4127 (1988).
K. Kim et al., Chem. Phys. lett. 228, 369 (1994).
c C. Dedonder-Lardeux et al., Phys. Chem, Chem, Phys. 3, 4316 (2001).
b S.
212
TK04
LASER DESORPTION SUPERSONIC JET SPECTROSCOPY OF HYDRATED TYROSINE
15 min 2:21
HIKARI OBA, YOKO SHIMOZONO, SHUN-ICHI ISHIUCHI, MASAAKI FUJII, Chemical Resources Lab.
Tokyo Tech. 4259 Nagatsuta-cho, Midoriku, Yokohama, 226-8503, Japan; PIERRE CARCABAL, ISMO.
Université Paris Sud XI Bâtiment 210, 91405, Orsay, Paris, France.
The structure of tyrosine (tyr) consists of amino-acid chain and phenol, and it has roughly two possible binding sites
for water, amino-acid site and phenolic OH site. Investigating how water molecule binds to tyr will give fundamental
information for hydrations of peptide and protein. Resonance enhanced multi photon ionization (REMPI) spectrum of tyrwater 1:1 cluster has already been reported by de Vries and co-workers,a however, no analysis on the hydrated structures
has been reported. In the REMPI spectrum, two clusters of bands are observed; one appears at ∼35600 cm−1 energy
region which is the almost same with 0-0 transitions of tyr monomer,b and another is observed at ∼300 cm−1 lower than
the former. Based on the electronic transition energy of phenylalanine and the hydrated clusters,c the former is expected
to be derived from a structure that water binds to amino acid site. On the other hand, it is plausibly predicted that the
latter originates from a structure that water binds to phenolic OH group, because the electronic transition of mono hydrated
phenol is ∼300 cm−1 red-shifted from the monomer.d We applied IR dip spectroscopy which can measure conformer
selective IR spectra to the tyr-(H2 O)1 clusters by using laser desorption supersonic jet technique to confirm the assignments.
Especially in the phenolic OH bound isomer, it was found that the intra molecular hydrogen bond within amino-acid chain,
which is far from the water molecule and cannot interact directly with each other, is strengthened by the hydration.
a A.
Abio-Riziq et al., J. Phys. Chem. A, 115, 6077 (2011).
Shimozono, et al., Phys. Chem. Chem. Phys., (2013) DOI: 10.1039/c3cp43573c.
c T. Ebata et al., Phys. Chem. Chem. Phys., 8, 4783 (2006).
d T. Watanabe et al., J. Chem. Phys., 105, 408 (1996).
b Y.
TK05
15 min 2:38
EXCITED-STATE DYNAMICS IN FOLIC ACID AND 6-CARBOXYPTERIN UPON UVA EXCITATION
HUIJUAN HUANG, R. AARON VOGT and CARLOS E. CRESPO-HERNÁNDEZ, Department of Chemistry and Center for Chemical Dynamics, Case Western Reserve University, Cleveland, Ohio 44106.
The excited-state dynamics of folic acid (FA) and 6-carboxypterin (6CP) are poorly understood and work is needed to uncover the relaxation pathways that ultimately lead to their oxidative damage of DNA. In our approach, broad-band transient
absorption spectroscopy was used to monitor the evolution of the excited states in FA and 6CP in basic aqueous solution
upon excitation at 350 nm. In addition, quantum-chemical calculations were performed to assist in the interpretation of the
experimental results and in the postulation of kinetic mechanisms. The combined experimental and computational results
support a kinetic model where excitation of FA results in ultrafast charge separation (τ = 0.6 ps), which decays back to
the ground state primarily by charge recombination with a lifetime of 2.2 ps. A small fraction of the charge transfer state
undergoes intersystem crossing to populate the lowest-energy triplet state with a lifetime of 200 ps. On the other hand, a
large fraction of the initially excited singlet state in 6CP decays by fluorescence emission with a lifetime of 100 ps, while
intersystem crossing to the triplet state occurs with a lifetime of 4.4 ns. The potential implications of these results to the
oxidative damage of DNA by FA and 6CP will be discussed. Funding from the National Science Foundation is gratefully
acknowledged (CHE-1255084).
213
TK06
15 min 2:55
RESONANCE ENHANCED MULTI-PHOTON IONIZATION (REMPI) AND DOUBLE RESONANCE (UV-UV AND
IR-UV) SPECTROSCOPIC INVESTIGATION ISOCYTOSINE
SEUNG JUN LEE, AHREUM MIN, AHREUM AHN, CHEOL JOO MOON, MYONG YONG CHOI, Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju
660-701, Korea; SHUN-ICHI ISHIUCHI, MITSUHIKO MIYAZAKI, MASAAKI FUJII, Tokyo Institute of
Technology, Chemical Resources Laboratory, Japan.
Isocytosine(iC), 2-aminouracil, is a non-natural nucleobase and its functional group’s positions resemble those of guanine; therefore, its spectroscopic investigation is worthy of attention especially for the natural/unnatural base pairs with
guanine and isoguanine. In this study, resonance enhanced multi-photon ionization (REMPI) and UV/IR-UV double resonance spectra of iC in the gas phase are presented. The collaboration work between Tokyo Institute of Technology, Japan
and Gyeongsang National University, Korea using laser ablation and thermal evaporation, respectively, for producing jetcooled iC is presented and discussed. The REMPI spectrum of iC monomers is recorded in the spectral range of 35000
to 36400cm-1, showing very congested -* vibronic bands. UV-UV hole burning spectroscopy is further conducted to investigate the conformational landscapes of iC monomers. Moreover, the presence of free OH band from IR-UV double
resonance spectroscopy in combination with quantum chemical calculations convinces that the iC monomer in free-jet
expansion experiment is an enol tautomer. However, a possible presence of a keto tautomer of iC may be provided by
employing a pico-second experiment on iC.
TK07
15 min 3:12
RESONANCE ENHANCED MULTI-PHOTON IONIZATION AND UV-UV HOLE-BURNING SPECTROSCOPIC
STUDIES OF JET-COOLED ACETANILIDE DERIVATIVES
CEOL JOO MOON and AHREUM MIN, AHREUM AHN, SEUNG JUN LEE, MYONG YONG CHOI, Department of Chemistry (BK21), Gyeongsang National University, 501 Jinju Daero, Jinju 600-701, South Korea; SEONG KEUN KIM, Department of Chemistry and Biophysics & Biophysical Chemistry (WCU) Seoul
National University, Seoul 151-747, South Korea.
Conformational investigations and photochemistry of jet-cooled methacetine (MA) and phenacetine (PA) using one color
resonant two-photon ionization (REMPI), UV-UV hole-burning and IR-dip spectroscopy are presented. MA and PA are
derivatives of acetanilide, substituted by methoxyl, ethoxyl group in the para position of acetanilide, respectively. Moreover, we have investigated conformational information of the acetanilide derivatives (AAP, MA and PA)-water. In this
work, we will present and discuss the solvent effects of the hydroxyl group of acetanilide derivatives in the excited state.
214
TK08
15 min 3:29
TAILOR MADE SYNTHESIS OF T-SHAPED AND π-STACKED DIMERS IN THE GAS PHASE: CONCEPT FOR
EFFICIENT DRUG DESIGN AND MATERIAL SYNTHESIS
SUMIT KUMAR and ALOKE DAS, Indian Institute of Science Education and Research (IISER), 900 NCL
Innovation Park, Dr. Homi Bhabha Road, Pune-411008, Maharashtra, India..
Non-covalent interactions play a key role in governing the specific functional structures of biomolecules as well as materials. Thus molecular level understanding of these intermolecular interactions can help in efficient drug design and material
synthesis. It has been found from X-ray crystallography that pure hydrocarbon solids (i.e. benzene, hexaflurobenzene)
have mostly slanted T-shaped (herringbone) packing arrangement whereas mixed solid hydrocarbon crystals (i.e. solid
formed from mixtures of benzene and hexafluorobenzene) exhibit preferentially parallel displaced (PD) π-stacked arrangement. Gas phase spectroscopy of the dimeric complexes of the building blocks of solid pure benzene and mixed benzenehexafluorobenzene adducts exhibit similar structural motifs observed in the corresponding crystal strcutures. In this talk,
I will discuss about the jet-cooled dimeric complexes of indole with hexafluorobenzene and p-xylene in the gas phase
using Resonant two photon ionzation and IR-UV double resonance spectroscopy combined with quantum chemistry calculations. In stead of studying benzene...p-xylene and benzene...hexafluorobenzene dimers, we have studied corresponding
indole complexes because N-H group is much more sensitive IR probe compared to C-H group. We have observed that
indole...hexafluorobenzene dimer has parallel displaced (PD) π-stacked structure whereas indole...p-xylene has slanted
T-shaped structure. We have shown here selective switching of dimeric structure from T-shaped to π-stacked by changing
the substituent from electron donating (-CH3) to electron withdrawing group (fluorine) in one of the complexing partners.
Thus, our results demonstrate that efficient engineering of the non-covalent interactions can lead to efficient drug design
and material synthesis.
Intermission
TK09
15 min 4:00
ROTATIONALLY RESOLVED HIGH-RESOLUTION LASER SPECTROSCOPY OF THE S1 ← S0 TRANSITION OF
NAPHTHALENE AND Cl-NAPHTHALENE
SHUNJI KASAHARA, RYO YAMAMOTO, KOHEI TADA, Molecular Photoscience Research Center, Kobe
University, Kobe 657-8501, Japan.
Rotationally resolved high-resolution fluorescence excitation spectra and the Zeeman effects of 0-0 band of S1 ← S0
electronic transition have been observed for naphthalene, 1-Cl naphthalene (1-ClN), and 2-Cl naphthalene (2-ClN). SubDoppler excitation spectra were measured by crossing a single-mode UV laser beam perpendicular to a collimated molecular beam. The typical linewidth was 25 MHz and the absolute wavenumber was calibrated with accuracy 0.0002 cm−1
by measurement of the Doppler-free saturation spectrum of iodine molecule and fringe pattern of the stabilized etalon. For
naphthalene a and 2-ClN, the rotationally resolved spectra were obtained, and these molecular constants were determined
in high accuracy. The obtained molecular constants of 2-ClN are good agreement with the ones reported by Plusquellic
et. al. b For 1-ClN, the rotational lines were not completely resolved because the fluorescence lifetime is shorter than the
one of 2-ClN. Additionally, we have observed the change of the spectra with magnetic field. The Zeeman broadening was
mainly observed for the levels of low Ka and increasing in proportion to J for given K for both of naphthalene and 2-ClN.
The order of magnitude and the J, K-dependence of the observed Zeeman broadening were similar to the other vibronic
bands of naphthalene. c
a D.
L. Joo, R. Takahashi, J. O’Reilly, H. Katô, and M. Baba, J. Mol. Spectrosc., 215, 155 (2002).
F. Plusquellic, S. R. Davis, and F. Jahanmir, J. Chem. Phys., 115, 225 (2001).
c H. Katô, S. Kasahara, and M. Baba, Bull. Chem. Soc. Jpn., 80, 456 (2007).
b D.
215
TK10
VIBRONIC SPECTROSCOPY OF 4-ISOCYANOBENZONITRILE
15 min 4:17
JOSEPH A. KORN, DEEPALI N. MEHTA-HURT and TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN,47907.
This talk will discuss the jet-cooled vibronic spectroscopy of 4-isocyanobenzonitrile (4IBN, CN-C6 H4 -CN) via resonant
two-photon ionization, laser induced fluorescence, dispersed fluorescence, and UV-UV hole burning methods. Much of
the vibronic spectroscopy of the molecule shows strong similarities with the symmetric structural isomers dicyano and diisocyanobenzene. However, in 4IBN, we have identified a series of weak transitions extending well red of the ππ* origin.
UV holeburning spectroscopy has been used to confirm that these transitions arise from the same ground state as the others,
pointing to the presence of another electronic state. Based on comparison with other nitrilebenzenes, we postulate that the
large dipole moment of 4IBN opens the possibility of a charge transfer (CT) state, much as occurs in para-amino substituted
benzonitriles. The rich vibronic spectroscopy of this molecule will be explored using dispersed fluorescence.
TK11
15 min 4:34
STEPWISE SOLVATION EFFECTS ON THE EXCITED STATES OF A WEAKLY COUPLED BICHROMOPHORE:
1,2-DIPHENOXYETHANE-(H2O)N (N=2-4) CLUSTERS
PATRICK S. WALSH, EVAN G. BUCHANAN, JOSEPH R. GORD and TIMOTHY S. ZWIER, Department
of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN 47907.
1,2-Diphenoxyethane (DPOE) is a prototypical flexible bichromophore which was shown to consist of two conformers in
the gas phase with the first two excited states split by 1 cm−1 or less.a Last year, we reported on the remarkable effects
of asymmetric binding of a single H2 O molecule to DPOE, localizing the electronic excitation, and producing OH stretch
IR spectra that report on the mixed electronic character of the excited state vibronic levels.b Here, we extend that work to
DPOE-(H2 O)n clusters with n=2-4 with the goal of seeing how the degree of asymmetry and electronic coupling evolve
as the number of water molecules bound to DPOE increases. Ground state IR spectra in the OH stretch region (3300-3750
cm−1 ) sensitively probe the H-bonding networks present in the clusters. In the excited states, the stepwise addition of
water molecules significantly changes the solvent-induced splitting of the excited states. Excited state IR spectroscopy is
used to identify the (nominal) S1 and S2 origins, and to track the degree of S1 /S2 character via the OH stretch transitions
observed. The spectra provide novel insight to the way in which solvent molecules redistribute the electronic energy as the
density of intermolecular vibrational modes grows with cluster size.
a E.
b E.
G. Buchanan, et al., J. Phys. Chem. A, submitted
G. Buchanan, et al., 67th International Symposium on Molecular Spectroscopy, 2012, WG08
216
TK12
15 min 4:51
PLANT SUNSCREENS IN NATURE: UV AND IR SPECTROSCOPY OF SINAPATE DERIVATIVES
JACOB C. DEAN, PATRICK S. WALSH, and TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN 47907; FLORENT ALLAIS, AgroParisTech, Paris, France.
Plants are exposed to prolonged amounts of UV radiation, with elevated levels of UV-B (280-320 nm) as the ozone layer
is depleted. When UV-B radiation penetrates the leaf epidermis, substantial oxidative damage can occur to plant tissues
and plant growth can be inhibited.a Sinapate esters, particularly sinapoyl malate, have been shown to efficiently prevent
such damaging effects. By studying a series of molecules in this unique class under the isolated, cold conditions of a
supersonic expansion, the fundamental UV-spectroscopic properties and photophysical aspects following UV absorption
can be interrogated in detail. Sinapic acid and neutral sinapoyl malate were brought into the gas phase by laser desorption and detected via resonant two-photon ionization (R2PI). IR-UV double resonance methods were employed to obtain
single-conformation UV and IR spectra. As the UV chromophore of interest is the sinapoyl moiety, sinapic acid served
as the simplest model to compare directly to the more functionalized sinapoyl malate. It has a spectrum much like most
aromatics, with a strong ππ ∗ origin, and well-resolved vibronic structure. By contrast, the spectrum for sinapoyl malate
displays a large, broad absorption with little resolved vibronic structure, reflecting its role in nature as a pivotal and efficient UV protectant for plants, serving as the plant’s sunscreen. Using conformer-specific IR spectroscopy, the individual
conformations of both species were assigned and used as the basis for further ab initio calculations of the excited states
that give rise to the observed behavior.
a Landry,
L.G.; Chapple, C.S.; Last, R.L. Plant Physiol. 1995, 109, 1159-1166.
TK13
15 min 5:08
FLUORESCENCE EXCITATION SPECTRA OF PHOTO-FRAGMENTED NITROBENZENE USING A PICOSECOND LASER: POTENTIAL EVIDENCE FOR NO PRODUCED BY TWO DISTINCT CHANNELS.
Upon absorption of a UV photon, nitrobenzene can dissociate into C6 H5 O and NO through two different mechanisms.
Evidence for these mechanisms was obtained from velocity map imaging (VMI) studies and theoretical calculations.a
VMI experiments showed NO produced with two distinct rotational distributions, which the calculations explained as a
fast and a slow channel for NO production. We have recorded high resolution fluorescence excitation spectra of the NO
resulting from photo-fragmented nitrobenzene using a pulsed picosecond tunable laser (pulse width ≈ 15 ps) by means of
a two-color process. In the two-color process, photons of a particular energy dissociated the nitrobenzene while photons
of a different energy probed the A2 Σ+ ← X 2 Π(1/2,3/2) NO band system between 225-260 nm. This laser system allowed
us to vary the delay between the photolysis and excitation pulses. At longer delays (>1 ns), we observed an increase in
the population of NO, which may be evidence that at least two photolysis channels produce NO. We present the spectra
we recorded at various photolysis/probe delays ranging from 0.025 to 1.5 ns. The spectral subtraction method we used to
observe the production increase is introduced.
a Hause,
M. L.; Herath, N.; Zhu, R.; Lin, M. C. and Suits, A. G. Nat Chem, Nature Publishing Group, 2011, 3, 932-937
217
TK14
SPECTROSCOPIC CHARACTERIZATION OF A NATURAL PRODUCT: ANETHOLE
15 min 5:25
VICTORIA P. BARBER AND JOSH J. NEWBY, Department of Chemistry and Biochemistry, Swarthmore
College, Swarthmore, PA 19081.
Anethole [(E)-1-methoxy-4-(1-propenyl)benzene] is a natural product molecule that is commonly recognized as the flavor
component of anise, fennel, and licorice. Early jet-cooled spectroscopy of anethole showed the existence of two possible
conformations, but did not address details of the vibronic structure.a Here, we report the jet-cooled, laser-induced fluorescence and single vibronic level fluorescence spectra of anethole. Analysis of the spectra confirms the existence of two
rotamers in the expansion that differ by the relative orientation of the methoxy and propenyl groups. The observed vibronic
activity is similar to that of styrene and indicates planar symmetry of both rotamers. Vibrational assignments of anethole
are assisted by density functional theory calculations and the results are compared with the analogous motions in styrene.
a V.
H. Grassian, E. R. Bernstein, H. V. Secor and J. I. Seeman J. Phys. Chem. 93, 3470 (1989).
218
WA. PLENARY
WEDNESDAY, JUNE 19, 2013 – 8:30 AM
Chair: ANNE MCCOY, The Ohio State University, Columbus, OH
WA01
40 min 8:30
CHARGE TRANSFER REACTIONS INDUCE BORN-OPPENHEIMER BREAKDOWN IN SURFACE CHEMISTRY:
APPLICATIONS OF DOUBLE RESONANCE SPECTROSCOPY IN MOLECULE-SURFACE SCATTERING
ALEC M. WODTKE, Georg-August University of Göttingen and the Max-Planck-Institute for Biophysical
Chemistry, Göttingen, Germany.
Atomic and molecular interactions constitute a many-body quantum problem governed fundamentally only by the Coulomb
forces between many electrons and nuclei. While simple to state, computers are simply not fast enough to solve this problem by brute force, except for the simplest examples. Combining the Born-Oppenheimer Approximation (BOA) with
Density Functional Theory (DFT), however, allows theoretical simulations of extraordinarily complex chemical systems
including molecular interactions at solid metal surfaces, the physical basis of surface chemistry. This lecture describes experiments demonstrating the limits of the BOA/DFT approximation as it relates to molecules interacting with solid metal
surfaces. One of the most powerful experimental tools at our disposal is a form of double resonance spectroscopy, which
allows us to define the quantum state of the molecule both before and after the collision with the surface, providing a
complete picture of the resulting energy conversion processes. With such data, we are able to emphasize quantitative measurements that can be directly compared to first principles theories that go beyond the Born-Oppenheimer approximation.
One important outcome of this work is the realization that Born-Oppenheimer breakdown can be induced by simple charge
transfer reactions that are common in surface chemistry.a
a J. D. White, J. Chen, D. Matsiev, D. J. Auerbach and A. M. Wodtke Nature 433(7025), 503-505 (2005);
Y. H. Huang, C. T. Rettner, D. J. Auerbach and A. M. Wodtke Science 290(5489), 111-114 (2000);
R. Cooper, I. Rahinov, Z. S. Li, D. Matsiev, D. J. Auerbach and A. M. Wodtke Chemical Science 1(1), 55-61 (2010;
J. Larue, T. Schäfer, D. Matsiev, L. Velarde, N. H. Nahler, D. J. Auerbach and A. M. Wodtke PCCP 13(1), 97-99 (2011).
WA02
40 min 9:15
ULTRA SENSITIVE CAVITY RING DOWN SPECTROSCOPY OF MAJOR ATMOSPHERIC SPECIES BETWEEN
1.20 AND 1.71 µm
A. CAMPARGUE, S. KASSI, and D. MONDELAIN, Université Grenoble 1/CNRS, UMR5588 LIPhy, Grenoble, F-38041, France.
During recent years, we have developed a fibered DFB laser CW-CRDS spectrometer providing routine noise equivalent
absorption of αmin ≈ 5 × 10−11 cm−1 , over the 5850-8350 cm−1 range. A detection limit of αmin ≈ 5 × 10−13 cm−1 has
been recently achieved by averaging spectra over a small spectral interval.
The performances of this set up have allowed extending significantly the knowledge of the absorption spectra of molecules
of major importance: methane, oxygen, water, ozone, carbon dioxide, hydrogen, nitrogen. The most striking results will
be presented.
Intermission
219
WA03
INFRARED STUDIES OF METAL CATION-DIHYDROGEN COMPLEXES
40 min
10:20
EVAN BIESKE, School of Chemistry, University of Melbourne, 3010, Australia.
Interactions between molecular hydrogen and metal cations play a key role in several contexts, including in the storage
of molecular hydrogen in zeolites, metal-organic frameworks, and doped carbon nano structures, in which dihydrogen is
typically attached to oxidised metal atoms. Arguably, the clearest view of the interaction between dihydrogen and a metal
cation is obtained by probing M+ -H2 complexes in the gas phase, free from the complicating influences of solvents or
substrates. To this end, we have used infrared spectroscopy to examine a series of M+ -H2 complexes, including complexes
containing alkali metals (Li+ -H2 , Li+ -D2 , Na+ -H2 , Na+ -D2 ), alkaline earth metals (Mg+ -H2 , Mg+ -D2 ), main group
metals and metalloids (B+ -H2 , B+ -D2 , Al+ -H2 ), and transition metals (Cr+ -D2 , Mn+ -H2 , Zn+ -D2 and Ag+ -H2 ). These
species have been characterized through their infrared absorptions in the H-H or D-D stretch regions (3700-4150 cm−1 and
2500-3000 cm−1 ranges, respectively) by monitoring metal cation photo-fragments as the infrared wavelength is scanned.
The spectra, which typically display full resolution of rotational structure, can be used to develop and test intermolecular
potential energy surfaces, and systematically explore the way in which the size and electronic structure of the metal cation
influences the properties of the intermolecular M+ · · · H2 bond.
WA04
SPECTROSCOPIC ENGINEERING IN THE SUBMILLIMETER
40 min
11:05
FRANK C. DE LUCIA, DEPARTMENT OF PHYSICS, OHIO STATE UNIVERSITY, COLUMBUS, OH
43210.
The field of high-resolution spectroscopy, as represented by the community that supports this meeting, has continued to
grow and prosper, in no small part because the field has continued to evolve. Much of this evolution could fall under
the rubric, Spectroscopic Engineering. This is especially true in the submillimeter where spectroscopists have taken on
much broader roles in fields that have grown out of submillimeter spectroscopy. With specific examples from spectroscopic remote and point sensing, astronomy and atmospheric science, imaging, and process control, opportunities and
paths forward for will be considered. Emphasis will be placed on the underlying physics that drives the optimization of
applications. Since this is Columbus, at least one complex Hamiltonian will be shown. We will also discuss: What are the
opportunities for young people entering the field and how might they be optimized? Is spectroscopy as a tool, less noble
than spectroscopy as a science? Is what we do really physics (or even chemistry)? Where does what we do fit into the
structure of academia, government, and industry?
220
WF. ASTRONOMICAL SPECIES AND PROCESSES
Chair: SANDRA BRUENKEN, University of Cologne, Koeln, Germany
WF01
RADIATIVE LIFETIME FOR NUCLEAR SPIN CONVERSION OF WATER-ION, H2 O
15 min 1:30
+
KEIICHI TANAKA, Department of Applied Chemistry, National Chiao Tung University, Hsinchu, 30010,
TAIWAN and Department of Chemistry, Faculty of Sciences, Kyushu University, Fukuoka, 812-8581 JAPAN;
KENSUKE HARADA, Department of Chemistry, Faculty of Sciences, Kyushu University, Fukuoka, 8128581 JAPAN; TAKESHI OKA, Department of Astronomy and Astrophysics and Department of Chemistry, the
Enrico Fermi Institute, the University of Chicago, Chicago, Illinois, 60637, USA.
Nuclear spin conversion interaction of the water ion, H2 O+ , has been studied to derive the spontaneous emission lifetime
between the ortho- and para-levels. The H2 O+ ion is a radical with 2 B1 electronic ground state and the off-diagonal
electron spin-nuclear spin interaction term, Tab (Sa ∆Ib + Sb ∆Ia ), connects para and ortho levels, because ∆I = I 1 − I 2
has nonvanishing matrix elements between I = 0 and 1. The Tab coupling constant, derived by an ab initio calculation in
MRD-CI/Bk level to be 72 MHz, is larger than that of H2 O by 4 orders of magnitude, makes the ortho to para conversion
of H2 O+ faster than that of H2 O by 8 orders of magnitude and possibly competitive with other astrophysical processes.
Last year we reported ortho and para coupling channels below 900 cm−1 caused by accidental near degeneracy of rotational
levels.a For example, hyperfine components of the 42,2 (o) and 33,0 (p) levels mix each other by 1.2 x 10−3 due to the near
degeneracy (∆E = 0.417 cm−1 ), but the lower lying 10,1 (p) and 11,1 (o) levels mix only by 8.9 x 10−5 because of their
large separation (∆E = 16.27 cm−1 ). In the present study, we solved the radiative rate equations including all the rotational
levels below 900 cm−1 to give the o-p conversion lifetime to be 0.451, 3.27, 398 and 910 years for the equilibrium o/p
ratio of 3.00, 3.00, 4.52, and 406 when the radiation temperature Tr is 100, 60, 20 and 5 K.
These results qualitatively help to understand the observed high o/p ratio of 4.8 ± 0.5 (corresponding to the nuclear spin
temperature of 21 K) toward Sgr B2,b but they are too slow to compete with the reaction by collision unless the number of
density of H2 in the region is very low (n ∼1 cm−3 ) or the radiative temperature is very high (Tr > 50K). c
a K.
Tanaka, K. Harada, and T. Oka, the 67th OSU Symposium MG06, 2012.
Schilke, et al., A&A 521, L11 (2010).
c K. Tanaka, K. Harada, and T. Oka, J. Phys. Chem. A, in press.
b P.
WF02
15 min 1:47
A MM/SUBMM WAVE SPECTROMETER TO QUANTIFY ASTROCHEMICAL REACTION RATES
JACOB C. LAAS and SUSANNA L. WIDICUS WEAVER, Department of Chemistry, Emory University, Atlanta, GA 30322.
Complex organic molecules (COMs) are being routinely detected at millimeter and submillimeter wavelengths toward
a variety of interstellar environments. There is a growing consensus that their formation is dominated by barrierless,
diffusion-limited addition reactions of radicals on icy grain surfaces. While astrochemical models have predicted the presence of many of these COMs, discrepancies have arisen between their observed and predicted relative abundances. It is
likely that these discrepancies arise from uncertainties in the rates for the dissociation reactions that form the precursor
radicals. More complete laboratory information is needed to improve the predictive power of astrochemical models of organic chemistry. We have developed a laboratory experiment that utilizes mm/submm wave direct absorption spectroscopy
to probe photodissociation branching ratios that are relevant to astrochemical models of complex organic chemistry. We
have benchmarked the performance of this spectrometer by examining the dissociation of methanol using a high-voltage
discharge source. We will report on these results, and the progress of utilizing this spectrometer for photodissociation
studies of COMs and COM precursors.
221
WF03
15 min 2:04
UNIFIED MICROSCOPIC-MACROSCOPIC MONTE CARLO SIMULATION OF ICE FORMATION ON INTERSTELLAR GRAINS
QIANG CHANG, Department of Chemistry, University of Virginia, Charlottesville, Virginia, USA; ERIC
HERBST, Department of Chemistry, Physics and Astronomy, University of Virginia, Charlottesville, Virginia,
USA.
Results of ice formation on interstelar grains by full microscopic-macroscopic Monte Carlo simulation of gas-grain chemistry in cold dense interstellar clouds are reported. Gas phase chemical kinetics is treated by macroscopic Monte Carlo
approach while reactions on grain are treated by microscopic Monte Carlo simulation. More than 200 diffusive surface
reactions are included in the simulation and we model how photons penetrate thick layers of species and photodissociate
species. Ice mantle on grain surfaces gradually build up as species accrete fron gas phase and react on the grain surface.
Photodissociated species are allowed to diffuse and react within ice mantle. Our results can be compared with observations.
WF04
15 min 2:21
THE LOW-TEMPERATURE NUCLEAR SPIN EQUILIBRIUM OF
H+
3
IN COLLISIONS WITH H2
FLORIAN GRUSSIE, MAX H. BERG, ANDREAS WOLF, and HOLGER KRECKEL, Max-Planck-Institut
für Kernphysik, 69117 Heidelberg, Germany; KYLE N. CRABTREEa and BENJAMIN J. McCALL, Department of Chemistry, University of Illinois, Urbana, IL, 61801; SABRINA GÄRTNER and STEPHAN
SCHLEMMER, I. Physikalisches Institut, Universität zu Köln, 50937 Köln, Germany.
Observations of H+
3 in diffuse molecular clouds have revealed that the ratio of its ortho and para nuclear spin modifications
are not in thermodynamic equilibrium with the environment. This discrepancy could be explained if the reaction H+
3 + H2
+
→ H2 + H+
,
which
interconverts
the
nuclear
spin
modifications
of
H
,
has
a
nonthermal
outcome
at
low
temperatures,
3
3
possibly arising from nuclear spin selection rules on systems of identical fermions. While the nuclear spin dependence of
this reaction has previously been investigated experimentally, the prior measurements were limited to temperatures above
∼130 K, well above the 50-70 K typical of diffuse molecular clouds.
+
To investigate whether the outcome of the H+
3 + H2 reaction is nonthermal, H3 ions were allowed to interact with H2
in the temperature-controlled environment of a 22-pole radiofrequency ion trap, and the relative abundances of orthoand para-H+
3 at steady state were measured using action spectroscopy. By carefully controlling the ortho:para ratio of
the H2 samples in conjunction with the ion trap temperature, the outcome of the reaction was observed to be close to
thermodynamic equilibrium over the temperature range of 45-100 K. Thus, the nonequilibrium ortho:para ratio of H+
3
observed in diffuse molecular clouds does not arise from a nonthermal outcome of the H+
3 + H2 reaction at low temperature.
This implies that the origin of the discrepancy lies in the respective formation and destruction mechanisms of H+
3.
a Present
address: Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, 02138
222
WF05
15 min 2:38
MOLECULAR HYDROGEN FORMATION : EFFECT OF DUST GRAIN TEMPERATURE FLUCTUATIONS
EMERIC BRON, JACQUES LE BOURLOT and FRANCK LE PETIT, LUTH - Observatoire de Paris, CNRS
UMR 8102, Université Paris Diderot. e-mail : [email protected].
H2 formation is a hot topic in astrochemistry. Thanks to Copernicus and FUSE satellites, its formation rate on dust grains
in diffuse interstellar gas has been inferred (Jura 1974, Gry et al. 2002). Nevertheless, detection of H2 emission in PDRs
by ISO and Spitzer (Habart et al., 2004, 2005, 2011 ) showed that its formation mechanism can be efficient on warm grains
(warmer than 30K), whereas experimental studies showed that Langmuir-Hinshelwood mechanism is only efficient in a
narrow window of grain temperatures (typically between 10-20 K). The Eley-Rideal mechanism, in which H atoms are
chemically bound to grains surfaces could explain such a formation rate in PDRs (Le Bourlot et al. 2012 ).
Usual dust size distributions (e.g. Mathis et al. 1977 ) favor smaller grains in a way that makes most of the available grain
surface belong to small grains. As small grains are subject to large temperature fluctuations due to UV-photons absorption,
calculations at a fixed temperature give incorrect results under strong UV-fields.
Here, we present a comprehensive study of the influence of this stochastic effect on H2 formation by LangmuirHinshelwood and Eley-Rideal mechanisms. We use a master equation approach to calculate the statistics of coupled
fluctuations of the temperature and adsorbed H population of a grain. Doing so, we are able to calculate the formation
rate on a grain under a given radiation field and given gas conditions. We find that the Eley-Rideal mechanism remains
an efficient mechanism in PDRs, and that the Langmuir-Hinshelwood mechanism is more efficient than expected on warm
grains.
This procedure is then coupled to full cloud simulations with the Meudon PDR code. We compare the new results with
more classical evaluations of the formation rate, and present the differences in terms of chemical structure of the cloud and
observable line intensities. We will also highlight the influence of some microphysical parameters on the results.
WF06
15 min 2:55
REVISED TERM VALUES FOR THE A − X (v = 0-9, v = 0) BANDS IN
SPECTRA ACQUIRED AT THE SOLEIL SYNCHROTRON
′
′′
13
C O FROM HIGH-RESOLUTION
16
L. GAVILAN, J. L. LEMAIRE, M. EIDELSBERG, Observatoire de Paris, Paris, France; S. R. FEDERMAN,
Department of Physics and Astronomy, University of Toledo, Toledo, OH 43606; G. STARK, A. N. HEAYS,
Department of Physics, Wellesley College, Wellesley, MA 02481; J. H. FILLION, Université PVI UMPC,
Paris, France; J. R. LYONS, IGPP, University of Califormia, Los Angeles, CA 90095; N. DE OLIVEIRA,
Synchrotron SOLEIL, Saint Aubin, France.
High-resolution spectra of the A 1 Π − X 1 Σ+ band system of 13 C16 O are presented. These were obtained with the VUV
Fourier transform spectrometer installed on the DESIRS beamline at the SOLEIL synchrotron. We provide revised term
values that extend to higher J ′ values than previous VUV measurements for most v ′ levels and lower J ′ values for v ′ = 0.
Previously observed perturbations of the rotational levels are confimed, but are seen now in greater detail, and evidence is
presented for new perturbations. The uncertainty in the line positions and term values of most CO transitions is estimated
to be within 0.01 cm−1 .
Intermission
223
WF07
15 min 3:30
PHOTOIONIZATION AND RECOMBINATION OF Ne IV AND EXCITATION OF NeV IN NEBULAR PLASMAS
SULTANA N. NAHAR, ETHAN PALAY, ANIL K. PRADHAN, Department of Astronomy, The Ohio State
The inverse processes of photoionization and electron-ion recombination are dominant in photoionized astrophysical plasmas. They determine the ionization fractions in photoionization equilibrium, physical conditions, and chemical abundances. We employ the unified theory of electron-ion recombination to study photoionization of Ne IV in photoionized
nebulae. That leads to the production of Ne V and spectral emission of forbidden optical and mid-infrared [Ne V] lines
via collisional excitation. These lines are prominent in the observations made by infrared space observatories SPITZER,
SOFIA, and HERSCHEL. The unified method for electronic recombination provides self-consistent data for photoionization and recombination that is necessary to eliminate uncertainties in the determination of ionization fractions. To wit:
Precise abundance of neon in the Sun is unknown owing to lack of accurate atomic data. A 20-level wave function expansion is used for the calculations of photoionization, recombination, and collisional excitation employing the relativistic
Breit-Pauli R-matrix method in the close coupling approximation. We find and delineate extensive resonance structures at
low energies that considerably enhance the effective cross sections and rates in astrophysical sources.
a
a Acknowledgement:
Partially supported by DOE and NSF. Computational work was carried out at the Ohio Supercomputer Center
WF08
15 min 3:47
THE ‘4050 Å GROUP’ OF THE Ã Πu - X̃
1
1
Σ+
g
TRANSITION SYSTEM OF C3
P.O. Box 9513, NL-2300 RA Leiden, the Netherlands; M. A. HADDAD, W. UBACHS, LaserLaB, VU University Amsterdam, De Boelelaan 1081, NL-1081 HV, Amsterdam, The Netherlands; M. R. SCHMIDT, Department of Astrophysics, N. Copernicus Astronomical Center, ul. Rabiańska 8, 87-100 Toruń, Poland;
J. KRELOWSKI, Centre for Astronomy, Nicolaus Copernicus University, Gagarina 11, 87-100 Toruń, Poland;
G. A. GALAZUTDINOV, Instituto de Astronomia, Universidad Catolica del Norte, Av. Angamos 0610,
Antofagasta, Chile.
The ‘4050 Å group’ of C3 , which consists of a series of bands of the Ã1 Πu - X̃1 Σ+
g electronic transition system, has
been of much interest to astronomers as it serves as a remote diagnostic of the physical-chemical conditions in translucent
interstellar clouds. In this contribution, we present:
a) The high resolution (R = 80 000) detection of eight vibronic bands of C3 in the diffuse translucent cloud towards
HD 169454. Four of these vibronic bands are also detected in two additional objects: HD 73882 and HD 154368. Column
densities and excitation conditions of C3 are inferred.
b) A laboratory re-examination of the eight vibronic bands observed towards HD 169454 using cavity ring-down spectroscopy and a supersonic plasma jet. High-quality laboratory data build the list of lines with a wavelength accuracy of
<0.01Å. This is sufficient for the analysis of the observational data. Improved spectroscopic parameters of the corresponding vibronic states are presented. An improved perturbation analysis in the Ã1 Πu (000) state is given as well.
13
c) The systematic laboratory investigation on the Ã1 Πu - X̃1 Σ+
C-substituted C3 .
g 000-000 electronic origin band of
13
Rotationally resolved spectra of all five C-isotopologues are recorded in a supersonic plasma expansion by discharging
13
C2 H2 or 12 C2 H2 /13 C2 H2 mixtures diluted in noble gas. The Ã1 Πu state molecular constants for all five isotopologues
and ground-state molecular constants for 13 C12 C13 C and 12 C13 C13 C are experimentally determined for the first time. This
work extends the recent mid-infrared work on the 13 C-isotopologues of C3 by Giesen et al.a
a T.
Giesen, private communication, December 2012.
224
WF09
15 min 4:04
A NEW METHODOLOGY FOR THE DETECTION OF LOW-ABUNDANCE SPECIES IN THE ISM:
DETECTION OF INTERSTELLAR CARBODIIMIDE (HNCNH)
Pasadena, CA 91125; RYAN A. LOOMIS, Department of Chemistry, University of Virginia, Charlottesville,
VA 22904; CAMERON M. CHARNESS, JOANNA F. CORBY, Department of Astronomy, University of Virginia, Charlottesville, VA 22904; GEOFFREY A. BLAKE, Division of Chemistry and Chemical Engineering
and Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125;
JAN M. HOLLIS, NASA Goddard Space Flight Center, Greenbelt, MD 20771; FRANK J. LOVAS, National
Institute of Standards and Technology, Gaithersburg, MD 20899; PHILIP R. JEWELL, and ANTHONY J.
REMIJAN, National Radio Astronomy Observatory, Charlottesville, VA 22903.
We present the first interstellar detection of carbodiimide (HNCNH) in observations towards Sgr B2(N) using data from the
publicly available Green Bank Telescope PRebiotic Interstellar MOlecular Survey project. Recent laboratory work predicts
an abundance of HNCNH of ∼10% of the abundance of its tautomer, cyanamide (NH2 CN), or ∼ 2 × 1013 cm−2 in Sgr
B2(N). Given this abundance at LTE conditions, the strongest rotational transitions of HNCNH have intensities at or below
the noise level of current observations of this source. A thermal population of HNCNH is therefore likely undetectable.
Instead, HNCNH is identified via maser emission features at centimeter wavelengths. This detection presents a new
methodology for the detection of low-abundance species and further demonstrates the power of cm-wave observations to
make definitive identifications based on a small number of observed features.
WF10
INDIRECT ROTATIONAL SPECTROSCOPY OF HCO
15 min 4:21
+
ADAM J. PERRY, JAMES N. HODGES, BRIAN M. SILLER, Department of Chemistry, University of Illinois, Urbana, IL 61801; BENJAMIN J. MCCALL, Departments of Chemistry, Astronomy, and Physics, University of Illinois, Urbana, IL 61801.
Molecular ions play important roles in astrochemistry and their spectroscopy is of great interest to astronomers who
try to detect these species in the interstellar medium and other astronomical environments. Only about 20 molecular
ions have been detected in outer space to date, mainly due to the lack of laboratory data which is required to support
astronomical observations. Not only is molecular ion spectroscopy inherently challenging, but so too is laboratory
THz spectroscopy, which necessitates an alternative approach to acquiring these laboratory spectra. We demonstrate a
method to indirectly measure the pure rotational spectra of molecular ions that is based on a combination differences
analysis of rovibrational transitions that typically lie in the mid-infrared, where laboratory spectroscopy is less challenging.
As a proof of concept, we present mid-infrared spectroscopy of the ν1 fundamental band of HCO+ , a well studied and
astronomically relevant ion, using Optical Heterodyne Velocity Modulation Spectroscopy (OHVMS) in conjunction with
an optical frequency comb for highly accurate and precise frequency calibration. Both P branch transitions out to P(10) and
R branch transitions out to R(9) have been measured. From these data we performed a combination differences analysis to
calculate the ground state rotational spectrum of HCO+ and compare it to the directly measured rotational spectrum. Here
the results of such an analysis will be presented as well as calculations for the v=1 vibrationally excited state rotational
spectrum.
225
WF11
15 min 4:38
SLIT-JET DISCHARGE STUDIES OF POLYACETYLENIC MOLECULES: SYNTHESIS AND HIGH RESOLUTION
INFRARED SPECTROSCOPY OF DIACETYLENE
Polyacetylenic molecules play an important role in both combustion chemistry as well as chemistry of the interstellar
medium. This talk presents first high resolution infrared spectroscopic efforts on the simplest jet-cooled polyacetylene,
namely diacetylene (C4 H2 ). Specifically, the fundamental anti-symmetric CH stretching mode (near 3333 cm−1 ) and several hot combination bands of diacetylene have been investigated under sub-Doppler, jet cooled conditions in a pulsed
supersonic slit discharge. Local Coriolis perturbations in the fundamental anti-symmetric CH stretch manifold are observed and analyzed. Six hot bands are observed, including the HCC bending mode (v 8 ) not observed in previous room
temperature studies.a The observation of these hot bands under rotationally jet cooled conditions (Trot =15.7(4) K) indicate
the presence of highly non-equilibrium relaxation processes between vibration and rotation.
a G.
Guelachvili, A. M. Craig, and D. A. Ramsay, J. Mol. Spectrosc. 105, 156 (1984)
WF12
15 min 4:55
SUB-DOPPLER SLIT JET DISCHARGE SPECTROSCOPY OF JET COOLED POLYACETYLENES: THE ANTISYMMETRIC CH STRETCH MODE OF TRIACETYLENE
Growth of polyacetylenic molecules in acetylene flames is thought to play a central role in combustion chemistry and formation of soot, as well as the chemistry of gas clouds in the interstellar medium. In this talk, we present results from first
sub-Doppler, high resolution infrared spectroscopic studies on triacetylene.a,b In particular, we explore the fundamental
anti-symmetric CH stretching mode (v 5 ) of jet-cooled triacetylene in a pulsed slit discharge, where the “in − situ synthesis” arises from a discharge of trace(0.1-1%) acetylene/rare gas mixtures followed by rapid CCH + HCCH chemistry
in the supersonic expansion environment. The band origin of this mode is determined to be 3329.0544(2) cm−1 . At high
resolution, a series of avoided energy level crossings arising from rotational perturbations are observed and ascribed to
perpendicular Coriolis mixing with a near degenerate manifold of Π vibrational symmetry. The energy level patterns are
successfully analyzed to reveal spectroscopic constants and Coriolis coupling matrix elements for the perturbing manifold.
In addition, a weak Π-Π hot band progression due to thermal population in the slit jet is observed and assigned.
a D.
b K.
McNaughton and D. N. Bruget, J. Mol. Spectrosc.150, 620 (1991)
Matsumura, K. Kawaguchi, D. McNaughton, and D. N. Bruget, J. Mol. Spectrosc.158, 489 (1993)
226
WF13
A LINE LIST FOR HYDROGEN SULFIDE
15 min 5:12
ALA’A A. A. AZZAM, SERGEI N. YURCHENKO, JONATHAN TENNYSON, Department of Physics and
Astronomy, University College London, London, WC1E 6BT, UK.
H2 S is being studied as part of the ExoMol project (www.exomol.com) with the aim of producing an accurate and comprehensive list of line positions and intensitiesfor temperatures up to 2000 K. This will provide an important resource
for atmospheric modelling of extrasolar planets and cool stars, as well as for the laboratory investigations and pollution
studies. A recently computed, variational ro-vibrational hot line list is presented. These computations used the DVR3Da
and potential energy surface (PES) refined to reproduce the measured data. An ab initio dipole moment surface (DMS) is
used for the transitions intensity calculations. Many dipole moment surfaces were constructed at different levels of theory and basis sets, and compared to the available intensity measurements. Our best surface was constructed at over 7000
geometries using CCSD(T)/aug-cc-pV(6+d)Z level of theory with added relativistic and core-electron corrections. The
anomalous behavior of H2 S intensities is well-knownb, and our calculations reproduce this behaviour quantitatively. O
With Martin-Drumel and Pirali, we have measured pure rotational transition frequencies of H2 S at room temperaturec in
the 45 to 360 cm−1 (1.4 to 10.5 THz) region using a Fourier transform spectrometer located at the AILES beamline of
the SOLEIL synchrotron. About 1700 lines were detected belonging to the ground vibrational state of H2 32 S, H2 33 S and
H2 34 S. 60% of these lines are recorded and assigned for the first time, sampling levels as high as J = 26 and Ka = 18.
Our variational calculations were used to identify 214 rotational lines of H2 32 S in its first excited bending vibrational state
for the first time.
a J.
Tennyson, M. A. Kostin, P. Barletta, G. J. Harris, O. L. Polyansky, J. Ramanlal and N. F. Zobov Comput. Phys. Commun.163(85), 2004.
Cours, P. Rosmus, and V. G. Tyuterev J. Chem. Phys. 117(223), 2002.
c A. A. A. Azzam, S. N. Yurchenko, J. Tennyson, M. Martin-Drumel and O. Pirali J. Quant.e Spectrosc. Radiat. Transf. (submitted) 2013.
b T.
WF14
ANALYSIS OF THE SUB-MILLIMETER ROTATIONAL SPECTRUM OF UREA
15 min 5:29
JESSICA R. THOMAS, ALYSSA M. FOSNIGHT, IVAN R. MEDVEDEV, Department of Physics, Wright
State University, 3640 Colonel Glenn Highway, Dayton, OH 45435, USA.
Urea, ((NH2 )2 CO), has broad presence in biological species. As a byproduct of human metabolism, this molecule is
commonly tested for in blood to diagnose different pathologies. Furthermore, urea is seen in interstellar medium and its
detection could yield valuable insight into the mechanisms governing star formation. Despite the prevalence of urea, an
absence exists in recorded frequencies of this molecule. The new generation of the sub-millimeter telescopes, such as
ALMA, HERSCHEL, and SOFIA, allows detection of interstellar molecular spectra at unprecedented spatial and spectral resolutions. The knowledge of the precise frequencies of spectra transitions present in interstellar molecular clouds
would alleviate the problem of spectral congestion and aid in molecular identification. This paper reports the most recent
investigation of the submillimeter/terahertz gas phase spectrum of urea. Up until now, only the microwave laboratory
spectrum of ureas vibrational ground state has been available. This paper reports the high-resolution spectra of urea in the
sub-millimeter range, and extends the spectroscopic assignment of the rotational transitions in the vibrational ground state.
Additionally, the assignment of the first vibrational state and tentative assignments of two additional vibrational states have
been made.
227
WF15
10 min 5:46
THE ROTATIONAL SPECTRUM OF COMPLEX ORGANIC MOLECULES: 2(N)-METHYLAMINOETHANOL
S. MELANDRI, A. MARIS and C. CALABRESE, Dipartimento di Chimica Ciamician, Università di
Bologna, via Selmi 2,40126 Bologna, Italy.
The detection of molecules in space, is based on their spectroscopic features and high resolution spectral data is needed
to allow an unambiguous identification of them. Many of the molecules detected in space are complex organic molecules
containing chains of carbon atoms and which therefore show a high degree of molecular flexibility. The high number of low
energy conformations and the presence of large amplitude motions on shallow potential energy surfaces are peculiar to this
kind of systems. The presence of a high number of stable conformers - often interconverting through small energy barriers
- usually gives rise to very complex spectra, which represent a challenge for spectroscopic and computational methods.
We report the rotational study of methylaminoethanol (MAE) performed by Free Jet Absorption Microwave Spectrocopy
(FJAMW). For this species it has proved essential to compute the complete potential energy surfaces related to the low
amplitude modes. This has been calculated at the B3LYP/6-311++G** level of theory while the stable geometries have
been characterized MP2/6-311++G**. The interest in the conformational properties of MAE is twofold: in the first place,
aminoethanol and thus also MAE can be considered precursors of aminoacids in the interstellar medium a and secondly,
the MAE side chain is present in important biological molecules such as adrenaline. The conformational preferences
of MAE are dominated by the intramolecular hydrogen bond between the OH and NH2 groups and its flexibility and
asymmetry generate a very high number of conformers. 24 stable conformations have been predicted and two conformers
were observed by FJAMW spectroscopy with our 60-72 GHz spectrometer. With respect to a previous studyb we have
extended the observed frequency range, partly reassigned the rotational spectrum of one of the conformers and determined
the nuclear quadrupole constants. The search for higher energy conformers has also been undertaken.
a S.
b R.
Charnley, in Proceedings of the workshop: The bridge between the Big Bang and Biology, CNR, Italy 1999.
E. Penn and L. W. Buxton J. Mol. Spectrosc. 56 229 1975.
228
WG. MINI-SYMPOSIUM: THEORY AND SPECTROSCOPY
Chair: G. BARNEY ELLISON, University of Colorado, Boulder, CO
WG01
INVITED TALK
30 min 1:30
COMBINING THEORY AND EXPERIMENT TO COMPUTE HIGHLY ACCURATE LINE LISTS FOR STABLE
MOLECULES, AND PURELY AB INITIO THEORY TO COMPUTE ACCURATE ROTATIONAL AND ROVIBRATIONAL LINE LISTS FOR TRANSIENT MOLECULES
TIMOTHY J. LEE, XINCHUAN HUANG, RYAN C. FORTENBERRY, Space Science and Astrobiology Division, NASA Ames Research Center; DAVID W. SCHWENKE, NAS Facility, NASA Ames Research Center.
Theoretical chemists have been computing vibrational and rovibrational spectra of small molecules for more than 40
years, but over the last decade the interest in this application has grown significantly. The increased interest in computing
accurate rotational and rovibrational spectra for small molecules could not come at a better time, as NASA and ESA
have begun to acquire a mountain of high-resolution spectra from the Herschel mission, and soon will from the SOFIA
and JWST missions. In addition, the ground-based telescope, ALMA, has begun to acquire high-resolution spectra in
the same time frame. Hence the need for highly accurate line lists for many small molecules, including their minor
isotopologues, will only continue to increase. I will present the latest developments from our group on using the "Best
Theory + High-Resolution Experimental Data" strategy to compute highly accurate rotational and rovibrational spectra for
small molecules, including NH3, CO2, and SO2. I will also present the latest work from our group in producing purely ab
initio line lists and spectroscopic constants for small molecules thought to exist in various astrophysical environments, but
for which there is either limited or no high-resolution experimental data available. These more limited line lists include
purely rotational transitions as well as rovibrational transitions for bands up through a few combination/overtones.
WG02
15 min 2:05
A NEW POTENTIAL ENERGY SURFACE FOR H2 –N2 O AND PIMC SIMULATION PROBING SUPERFLUIDITY
AND VIBRATIONAL FREQUENCY SHIFTS IN DOPED para-H2 CLUSTERS
LECHENG WANG, ROBERT J LE ROY AND PIERRE-NICHOLAS ROY, Guelph-Waterloo Centre for
Graduate Work in Chemistry and Biochemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada;
DAIQIAN XIE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu, China.
The existence of superfluidity of para-hydrogen clusters doped by the linear moleculesa,b,c such as CO, CO2 and OCS
stimulated our theoretical study of (para-H2 )N –N2 O clusters. A new 6D ab initio PES for the H2 –N2 O dimer which
explicitly included the symmetric and asymmetric vibrational coordinates Q1 and Q3 of N2 O was constructed. Fourdimensional global intermolecular PESs were then obtained by fitting the vibrational averaged interactions energies for
ν3 (N2 O)=0 and 1 to the Morse/Long Range(MLR) analytical form with theoretically fixed long-range parameters. Using
the adiabatic hindered-rotor approximation, effective two-dimensional PESs for the para-H2 –N2 O dimer were then generated. Predictions of the infrared spectra of para-H2 –N2 O based on these PESs have been in good agreement with the
experimental observations.d Based on these surfaces, predictions of structural properties, vibrational band origin shifts,
rotational dynamics and superfluidity of (para-H2 )N –N2 O clusters have been generated using bosonic PIMC simulation
methods. The evolution of the calculated shifts agreed reasonably with that for the experimental observations.e Reduction
of the effective moment of inertia is predicted to occur when the dopant is partially surrounded by the para-H2 solvent,
which marked the onset of molecular superfluidity in para-H2 . Results obtained using our surfaces and PIMC algorithm
will be presented.
a
H. Li, R. J. Le Roy, P.-N. Roy and A.R.W. McKellar, Phys. Rev. Lett. 105, 133401 (2010).
S. Grebenev, B. G. Sartakov, J. P. Toennies and A. F. Vilesov, J. Chem. Phys. 132, 064501 (2010).
c P. L. Raston, W. Jager, H. Li, R. J. Le Roy, and P.-N. Roy , Phys. Rev. Lett. 108, 253402 (2012).
d J. Tang and A.R.W. McKellar, J. Chem. Phys. 117, 8308 (2002).
e J. Tang and A.R.W. McKellar, J. Chem. Phys. 123, 114314 (2005).
b
229
WG03
SUPERFLUIDITY HIDDEN IN A FORGOTTEN CORNER
15 min 2:22
TAO ZENG, GREGOIRE GUILLON, and PIERRE-NICHOLAS ROY, Department of Chemistry, University
of Waterloo, Waterloo, Ontario, Canada N2L 3G1.
In 1998, Grebenev et al. [S. Grebenev, J. P. Toennies, and A. F. Vilesov, Science, 279, 2083-2086 (1998)]] successfully
conducted a spectroscopic Andronikashvili experiment to detect the superfluid response of a 4 He cluster with about only
60 atoms to the rotation of an embedded OCS chromophore. This success led to a new wave of investigations in the area of
microscopic superfluidity. 4 He droplets and para-H2 clusters exhibit this special phenomenon through their non-classical
moments of inertia (NCMI) when they are dragged to rotate with a dopant. So far, all the studies are devoted to the
diagonal elements of the moment of inertia tensor of the dopant and investigate how they are affected by the surrounding
microscopic superfluids. In this way, the tensorial character of the moment of inertia has been ignored. We hereby report
the first-ever study on the superfluid information conveyed by the off-diagonal elements of the moment of inertia tensor.
We study the rotation of a methyl formate (HCOOCH3 ) molecule doped in 4 He clusters. The Cs symmetry of HCOOCH3
guarantees an off-diagonal moment of inertia tensor, and we found that the off-diagonal terms render superfluid information
through the orientation of the principal-axes of the effective rotor with the surrounding 4 He atoms. This is a new piece
of information extracted from the corners of the moment of inertia tensor. Technically, we have developed a symmetryadapted path-integral Monte Carlo (SA-PIMC) program to simulate the HCOOCH3 (4 He)N clusters. This new algorithm
leads to a better convergence of our simulations.
WG04
15 min 2:39
COMPUTATIONAL FRAMEWORK FOR STUDYING H-BONDING IN THE OH STRETCH REGION OF VIBRATIONAL SPECTRA
LAURA C. DZUGAN and ANNE B. McCOY, Department of Chemistry and Biochemistry, The Ohio State
In many H-bonded complexes, there are two types of bands in the OH stretch region of the vibrational spectra; narrow
peaks due to isolated OH stretches and a broadened feature reflecting hydrogen bonding. This second region can be
as wide as several hundred wavenumbers and is shifted to the red of the narrow peaks. Furthermore, the extent of this
broadening depends on system size and geometry. In this work we focus on (CaOH)+ ·(H2 O)n systems. For example,
when n=4, the hydrogen bonding feature is several hundred wavenumbers. This is indicative of coupling between the OH
stretches of the water molecules to the low frequency modes. To understand the broadening observed in the spectra, we
have developed a computational framework in which we convolute the harmonic spectra of the OH stretches evaluated over
the range of sampled intermolecular geometries. This framework will be discussed in context of several systems, including
(CaOH)+ ·(H2 O)n .
230
WG05
15 min 2:56
ESR SPECTRA OF ALKALI-METAL ATOMS ON HELIUM NANODROPLETS: A THEORETICAL MODEL FOR
THE PREDICTION OF HELIUM INDUCED HYPERFINE STRUCTURE SHIFTS
ANDREAS W. HAUSER, Institute of Experimental Physics, Graz University of Technology, Petersgasse
16, A-8010 Graz, Austria; MICHAEL FILATOV, Mulliken Center for Theoretical Chemistry, Institut
für Physikalische und Theoretische Chemie, Universität Bonn, Beringstrasse 4, 53115 Bonn, Germany;
WOLFGANG E. ERNST, Institute of Experimental Physics, Graz University of Technology, Petersgasse 16,
A-8010 Graz, Austria.
We predict He-droplet-induced changes of the isotropic HFS constant aHF S of the alkali-metal atoms M = Li, Na, K and
Rb on the basis of a model description. Optically detected electron spin resonance spectroscopya has allowed high resolution measurements that show the influence of the helium droplet and its size on the unpaired electron spin density at the
alkali nucleusb . Our theoretical approachc to describe this dependence is based on a combination of two well established
techniques: Results of relativistic coupled-cluster calculations on the alkali-He dimers (energy and HFS constant as functions of the binding length) are mapped onto the doped-droplet-situation with the help of helium-density functional theory.
We simulate doped droplets HeN with N ranging from 50 to 10000, using the diatomic alkali-He-potential energy curves
as input. From the obtained density profiles we evaluate average distances between the dopant atom and its direct helium
neighborhood. The distances are then set in relation to the variation of the HFS constant with binding length in the simplified alkali-He-dimer model picture. This method yields reliable relative shifts but involves a systematic absolute error.
Hence, the absolute values of the shifts are tied to one experimentally determined HFS constant for 85 Rb-HeN = 2000 . With
this parameter choice we obtain results in good agreement with the available experimental data for Rb and Ka,b confirming
the predicted 1/N trend of the functional dependencec.
a M.
Koch, G. Auböck, C. Callegari, and W. E. Ernst, Phys. Rev. Lett. 103, 035302-1-4 (2009)
Koch, C. Callegari, and W. E. Ernst, Mol. Phys. 108 (7), 1005-1011 (2010)
c A. W. Hauser, T. Gruber, M. Filatov, and W. E. Ernst, ChemPhysChem (2013) online DOI: 10.1002/cphc.201200697
b M.
WG06
15 min 3:13
Xe AND Rb ATOMS ON HELIUM NANODROPLETS: IS THE VAN DER WAALS ATTRACTION STRONG ENOUGH
TO FORM A MOLECULE?
JOHANNES POMS, ANDREAS W. HAUSER and WOLFGANG E. ERNST, Institute of Experimental
Physics, Graz University of Technology, Petersgasse 16, A-8010 Graz, Austria.
Chemical reactions in the cold environment of a helium nanodroplet currently attract high interest and can be spectroscopically observed with typical molecular beam techniquesa. In order to estimate the influence of surrounding helium on
the van der Waals interaction between heliophilic and heliophobic dopants that could be investigated in our lab with ESR
spectroscopyb, we apply density-functional theory to simulate a double-dotation of He-clusters with Rb and Xe atoms.
Simulations of a double-doped HeN droplet with N = 500 show that the alkali metal atom stays on the surface, whereas
the Xe atom sits in the middle of the droplet. The van der Waals attraction between Rb and Xe is not strong enough to
compensate the separation of the heliophilic Xe and the heliophobic Rb caused by the helium droplet: a potential barrier
of 23.4 K has to be overcomec, which is to be compared with the 0.4 K internal temperature of the droplet.
in: Handbook of High-Resolution Spectroscopy, eds. M. Quack and F. Merkt, John Wiley & Sons, Chichester (2011)
b M. Koch, C. Callegari, and W. E. Ernst, Mol. Phys. 108 (7), 1005-1011 (2010)
c J. Poms, A. W. Hauser, and W. E. Ernst, Phys. Chem. Chem. Phys. 14, 15158-15165 (2012)
Intermission
231
WG07
15 min 3:45
RENNER-TELLER COUPLING IN OPEN SHELL DIHYDRIDES: A COMPARISON OF THEORY WITH OPTICAL
SPECTRA OF NEUTRAL AND IONIC MOLECULES
G. DUXBURY, Department of Physics, SUPA, John Anderson Building, University of Strathclyde, 107 Rottenrow, Glasgow G4 0NG, Scotland, UK; Ch. JUNGEN, LAC, 1Laboratoire Aime Cotton du CNRS, Universite
de Paris-Sud, 91405 Orsay, France; A. ALIJAH, GSMA, UMR CNRS 6089, Universite de Reims ChampagneArdenne,B.P. 1039, 51687 Reims Cedex 2, France.
The studies of the Renner-Teller coupling in isoelectronic series of the neutral dihydrides, started with the experiments of
Dressler and Ramsay a on the absorption spectra of NH2 and of ND2 published in 1959, with a companion paper on the
theory by Pople and Longuet Higgins b . Subsequently experiments on their ionic counterparts, e.g. H2 O+, were carried out,
initially using photoelectron spectroscopy. However it was not until the period starting in 1965 to 1980 that methods for
calculating the vibronic interaction between the half-states were derived and tested. Complications arise owing the the role
of the linear degeneracy of the two half states in the formation of the rovibronic structure, and the effects of the increasing
spin-orbit interaction in the series from NH2 to SbH2 , and H2 O+ to H2 Se+ in facilitating fragmentation processes. Many of
these molecular spectra were considered in great detail, but some, such as that of AsH2 , have had a less complete treatment
of vibronic interaction, in part since the original study of its electronic spectrum took place in the period from 1966-67
before most of the vibronic coupling methods had been developed developed. We wish to show the interplay between the
angular momentum effects caused by the large amplitude motion in a degenerate system, and those caused by a rapidly
increasing spin-orbit coupling constant.
a Phil.
Trans. Roy. Soc. 251,553(1959)
Phys. 1,372(1958)
b Molec.
WG08
RENNER-TELLER AND SPINORBIT COUPLING IN H2 S+ AND AsH2
15 min 4:02
G. DUXBURY, Department of Physics, SUPA, John Anderson Building, University of Strathclyde, 107 Rottenrow, Glasgow G4 0NG, Scotland,UK ; Ch. JUNGEN, LAC, 1Laboratoire Aime Cotton du CNRS, Universite
de Paris-Sud, 91405 Orsay, France; A. ALIJAH, GSMA, UMR CNRS 6089, Universit de Reims ChampagneArdenne,B.P. 1039, 51687 Reims Cedex 2, France.
The semi-rigid bender approach of Dixon and Duxbury,a and the alternative approach by Jungen and Mererb were devised
to minimise the effects of the large amplitude bending upon the Renner-Teller interaction. They also allow the effects of
large amplitude motion on the rotational structure to be calculated, including the switchover from bent to linear behaviour.
From this the stretch-bender reference-frame c were developed to allow the separation of large amplitude bending motion
and symmetric stretching. It has been used to calculate vibrational resonances, the effects of spin-orbit coupling, and of
overall rotation. As both states are derived from the degenerate π state of the linear molecule, we wish to show the utility of
this approach to understanding the large interaction between the high lying bending levels of the the electronic ground state
and the low lying levels of the excited state, including the predissociation of higher vibronic levels, of H2 S+ and AsH2 .
a Molec.
Phys. 43,255(1981)
Phys. 40,1(1981)
c J. Chem. Phys. 108,2336 (1998) and J. Mol. Spectrosc. 211,7 (2002)
b Molec.
232
WG09
15 min 4:19
COMPUTING ROVIBRATIONAL LEVELS OF POLYATOMIC MOLECULES WITH CURVILINEAR INTERNAL VIBRATIONAL COORDINATES AND AN ECKART FRAME
Kingston, Canada.
We present a new procedurea for computing a rovibrational spectrum of a polyatomic molecule. The Schrödinger equation is solved, numerically exactly, by using a nested contracted basis. Rovibrational wavefunctions are computed in a
|vi|JKM i basis, where |vi is a vibrational wavefunction and |JKM i is a symmetric top wavefunction. In turn, the
|vi are obtained by solving a vibrational Schrödinger equation with basis functions that are products of contracted bend
and stretch functions. At all stages of the calculation we exploit parity symmetry. The calculations are done in internal
coordinates that facilitate the treatment of large amplitude motion. An Eckart molecule-fixed frame is used by numerically computing coefficients of the kinetic energy operator.b The method is significantly more efficient than the previous
methodc which uses a molecule-fixed frame attached to two vectors and vibrational basis functions that depend on K. The
efficacy of the method is demonstrated by calculating a large number of converged J = 10 methane rovibrational levels
in the Tetradecad polyad (vibrational energies in the range 5100 - 6100 cm−1 ). No previous calculation of rovibrational
levels of methane includes as many levels as we report in this paper.
a X.-G.
Wang and T. Carrington, Jr., J. Chem. Phys. 138, 000000 (2013).
B. McCoy, D. C. Burleigh, and E. L. Sibert, J. Chem. Phys. 95, 7449 (1991).
c X.-G. Wang and T. Carrington, Jr., J. Chem. Phys. 121, 2937 (2004).
b A.
WG10
AN ACCURATE POTENTIAL ENERGY SURFACE FOR METHANE
15 min 4:36
Kingston, Canada.
An accurate full dimensional methane potential energy surface (PES) will aid in assigning and understanding its complicated spectrum. Heretofore, there is no pure ab initio PES of methane on which rovibrational levels have errors less than
one cm−1 . In this work, we obtain an accurate methane PES by starting with the ab initio PES of Schwenke and Partridge
[Spectrochim. Acta A 57, 887 (2001)] and adjusting 5 of their parameters to reproduce 39 reliable vibrational levels of
CH4 . This reduces the rmsd from 4.3 cm−1 to 0.4 cm−1 . Since not all of the Tetradecad levels are certain, only 4, those
confirmed by direct experimental transitions, are included in the fit. The new PES ought therefore to aid in the ongoing
analysis of the Tetradecad polyad. To further test the accuracy of the new PES, vibrational and rovibrational levels are
computed for CH4 , CH3 D, CHD3 and CH2 D2 and are compared with the extensive experimental data. The errors are all
within about one cm−1 .
The fitting is made possible by a contracted-iterative methoda for computing vibrational levels in a product of contracted
stretch and bend functions. The fitting process is efficient because these contracted basis functions are not changed during
the fitting cycles, which greatly reduces the time (to about 3 hours) to compute a new set of vibrational levels when the
PES is slightly changed.
a X.-G.
Wang and T. Carrington, Jr., J. Chem. Phys. 119, 101 (2003).
233
WG11
15 min 4:53
THEORETICAL CALCULATIONS AND SIMULATIONS OF INTERACTION OF X-RAYS WITH HIGH-Z
NANOMOITIES FOR USE IN CANCER RADIOTHERAPY
SARA N. LIM, Biophysics Graduate Program; ANIL K. PRADHAN, Biophysics Graduate Program, Chemical Physics Program and Department of Astronomy, The Ohio State University; SULTANA N. NAHAR,
Astronomy, The Ohio State University.
When used with X-ray radiotherapy, heavy elements (high atomic number Z or HZ) such as gold(Au) and platinum(Pt) have
the potential to greatly sensitize and enhance the damage to tumor tissues. While HZ radiosensitization has been shown
to be higly effective in reducing tumor sizes, much work still needs to be done to determine the ideal X-ray energy/energy
spectrum. The likelihood of photoelectric absorption of X-rays that result in the production of cell-killing Auger electrons
relative to the photon scatter in an HZ sensitized tumor has to be determined for treatments using X-rays from various
sources and energies to assess their efficacy. In this report, we present computations that outline the dependence of photoelectric absorption on X-ray energy. The relative X-ray absorption by a radiosensitized tumor was calculated to contrast
the efficacy of different X-ray sources in Auger electron production at different tumor depths. Enhanced photoabsorption
of low-energy X-rays from broadband sources in the keV range is shown to be much higher than from those in the MeV
range. In addition, with the use of the Monte Carlo code package Geant4, we present the total X-ray energy deposited into
a radiosensitized tumor located at different depths in a phantom. The enhancement in radiation dose deposition will also
be analysed at the microscopic cellular level to determine the HZ radiosensitizer concentration required. Potential use of
monochromatic X-rays for more precise HZ radiosensitization will also be described.
WG12
15 min 5:10
SUPERIORITY OF LOW ENERGY 160 KV X-RAYS COMPARED TO HIGH ENERGY 6 MV X-RAYS IN HEAVY
ELEMENT RADIOSENSITIZATION FOR CANCER TREATMENT
SARA N. LIM, Biophysics Graduate Program; ANIL K. PRADHAN, Biophysics Graduate Program, Departments of Astronomy and Chemistry; SULTANA N. NAHAR, Department of Astronomy; ROLF F. BARTH,
WEILIAN YANG, ROBIN J. NAKKULA, Pathology, The Ohio State University; ALYCIA PALMER and
CLAUDIA TURRO, Department of Chemistry, The Ohio State University.
High energy X-rays in the MeV range are generally employed in conventional radiation therapy from linear accelerators
(LINAC) to ensure sufficient penetration depths. However, lower energy X-rays in the keV range may be more effective
when coupled with heavy element (high-Z or HZ) radiosensitizers. Numerical simulations of X-ray energy deposition
for tumor phantoms sensitized with HZ radiosensitizers were performed using the Monte Carlo code Geant4. The results
showed enhancement in energy deposition to radiosensitized phantoms relative to unsensitized phantoms for low energy
X-rays in the keV range. In contrast, minimal enhancement was seen using high energy X-rays in the MeV range. Dose
enhancement factors (DEFs) were computed and showed radiosensitization only in the low energy range < 200 keV, far
lower than the energy of the majority of photons in the LINAC energy range. In vitro studies were carried to demonstrate
the tumoricidal effects of HZ sensitized F98 rat glioma cells following irradiation with both low energy 160 kV and high
energy 6 MV X-ray sources. The platinum compound, pyridine terpyridine Pt(II) nitrate, was initially used because it was
7x less toxic that an equivalent amount of carboplatin in vitro studies. This would allow us to separate the radiotoxic and
the chemotoxic effects of HZ sensitizers. Results from this study showed a 10-fold dose dependent reduction in surviving
fractions (SF) of radiosensitized cells treated with low energy 160 kV X-rays compared to those treated with 6 MV Xrays. This is in agreement with our simulations that show an increase in dose deposition in radiosensitized tumors for low
energy X-rays. Due to unforeen in vivo toxicity, however, another in vitro study was performed using the commonly used,
Pt-based chemotherapeutic drug carboplatin which confirmed earlier results. This lays the ground work for a planned in
vivo study using F98 glioma bearing rats. This study demonstrates that while high energy X-rays are commonly used in
cancer radiotherapy, low energy keV X-rays might be much more effective with HZ radiosensitization.
234
WG13
ALKYL CH STRETCH VIBRATIONS AS A PROBE OF CONFORMATIONAL PREFERENCES
15 min 5:27
EDWIN L. SIBERT III, Department of Chemistry and Theoretical Chemistry Institute, University of
Wisconsin-Madison, WI 53706; EVAN G. BUCHANAN AND TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN 47907-2084.
Theoretical IR spectra of 1,2-diphenoxyethane (C6 H5 -O-CH2 -CH2 -O-C6 H5 DPOE) and 1,2-diphenylethane (C6 H5 -CH2 CH2 -C6 H5 DPE) are presented and compared to results of single-conformation spectroscopy of jet cooled molecules. The
theoretical transition energies and intensites are obtained from a model based on a local mode Hamiltonian that includes
all local cubic stretch-bend couplings that are then projected onto the normal modes. The model parameters are obtained
from density functional theory methods. Full dimensional calculations are compared to those of reduced dimensions
that include anharmonic CH streches Fermi coupled to scissor modes. Excellent agreement is found. Scale factors of
select terms in the reduced dimensional Hamiltonian are determined by fitting the theoretical Hamiltonian to the anti DPE
spectrum. Using the same scaling, Hamiltonians for other conformers of the above molecules are generated and used to
predict structures by comparing to experimentally determined spectra in the alkyl CH stretch region. The level patterns
in the resulting spectra are elucidated in terms of the model parameters. The model results are extended to interpret the
spectra of more complicated macrocycles containing multiple -CH2 CH2 - ethano bridges such as the dibenzo-15-crown-5
ether and 2,2,2-paracyclophane.
WG14
THEORETICAL STUDY OF THE VIBRATIONAL SPECTROSCOPY OF THE ETHYL RADICAL
15 min 5:44
DANIEL P. TABOR and EDWIN. L. SIBERT III, Department of Chemistry and Theoretical Chemistry Institute, University of Wisconsin-Madison, Madison, WI 53706.
The rich spectroscopy of the ethyl radical has attracted the attention of several experimentalab and theoretical investigations.c The purpose of these studies was to elucidate the signatures of hyperconjugation, torsion, inversion, and Fermi
coupling in the molecular spectra. Due to the number of degrees of freedom in the system, previous theoretical studies
have implemented reduced-dimensional models. Our ultimate goal is a full-dimensional theoretical treatment of the vibrations using both Van Vleck and variational approaches. The methods will be combined with the potential that we have
calculated using the CCSD(T) method on the cc-pVTZ basis set. In this talk we will discuss our initial work, which builds
up from these reduced-dimensional models. Our calculations use coordinates that exploit the system’s G12 PI symmetry in
a simple fashion. By systematically adding more degrees of freedom to our model, we can determine the effects of specific
couplings on the spectroscopy.
a T.
Häber, A. C. Blair, D. J. Nesbitt and M. D. Schuder J. Chem. Phys. 124, 054316, (2006).
.E. Douberly, unpublished.
c R. S. Bhatta, A. Gao and D. S. Perry J. Mol. Struct.: THEOCHEM 941, 22, (2010).
bG
235
WG15
15 min 6:01
SIMULATION OF HIGH RESOLUTION VIBRATIONAL AND ELECTRONIC SPECTRA WITH A MULTIFREQUENCY VIRTUAL SPECTROMETER
Moving from the common practice of extracting numerical data from experiment
to be compared with quantum mechanical (QM) results toward a direct vis-à-vis
11B1←11A1
comparison of experimental and simulated spectra would strongly reduce any
ν9+ν7 2ν9+ν7
arbitrariness in analysis of complex experimental outcomes and allow a proper
ν7 2ν9
account of the information connected to both position and shape of spectral bands.
ν9
The development of such “virtual ab initio spectrometers” for a wide range of
wavelengths has been one of our major research goals in the last years [1,2]. Recent
methodological advances from our group allow simulation of optical (IR, Raman,
UV-vis, etc.) spectra line-shapes for medium-to-large closed- and open-shell
molecular systems. Vibrational spectra are computed including anharmonicities
-1
through perturbative corrections while electronic spectra line-shapes are simulated
accounting for the vibrational structure. Well resolved and accurate theoretical
spectra provide data as close as possible to the results directly available from experiment allowing to avoid ambiguities
in analysis of the latter. Several examples illustrating interpretation, assignment or revision of experimental spectra for
prototypes of bio-molecular systems (phenyl radical, glycine, thymine, pyrimidine, anisole dimer) will be presented.
1. V. Barone, A. Baiardi, M. Biczysko, J. Bloino, C. Cappelli, F. Lipparini Phys. Chem. Chem. Phys, 14, 12404, 2012
2. M. Biczysko, J. Bloino, G. Brancato, et al. Theor. Chem. Acc. 113, 1201, 2012
236
WH. MICROWAVE
Chair: NICHOLAS WALKER, Newcastle University, Newcastle-upon-Tyne, United Kingdom
WH01
THE LATEST REVISION OF THE ERHAM CODE
15 min 1:30
P. GRONER, Department of Chemistry, University of Missouri-Kansas City, Kansas City, MO 64110-2499.
ERHAM is a program based on the Effective Rotational Hamiltonian for molecules with two periodic large-amplitude
internal motions that can also be used for molecules with just one internal rotor.a A new version of the program is now
available on the PROSPE web site.b The recent modifications including a correction and some new features are described
in this presentation. They are:
1. The relative intensities have been corrected and now are calculated as Irel = S ∗ µ2 ∗ exp(−El /kT ) ∗ (1 −
exp(−hν/kT )) ∗ ν . The intensity threshold for printing now applies to Irel as given above instead to S ∗ µ2 .
2. There is a new option to generate an additional file containing the predictions in the JPL catalog file format.
3. During the prediction, the program automatically acquires the rotational partition function by summation if the minimum
of the range of J is 0, but only up to the maximum of the range. This required a revised definition of the - signs printed
for some energy levels during the prediction to ensure that the partition function acquisition works with the correct spin
weights.
4. Scaling factors for the spectroscopic parameters are used during the least-squares fit to help alleviate problems that
occasionally affected the inversion of the normal matrix. This feature has improved the convergence of the least-squares
fit in some cases.
5. The upper limit of the number of tunneling parameters per state has been increased to 37 (up from 31). The dimensions
of arrays have been increased to allow to order up to 140000 predicted transitions (up from 50000).
a P.
b Z.
Groner, J. Chem. Phys. 107, 4483 (1997); J. Mol. Spectrosc. 278, 52 (2012).
Kisiel, http://www.ifpan.edu.pl/∼kisiel/prospe.htm
WH02
10 min 1:47
GENERALIZED EQUATIONS FOR THE INERTIAL TENSOR OF A WEAKLY BOUND COMPLEX
KENNETH R. LEOPOLD, Department of Chemistry, University of Minnesota, 207 Pleasant St., SE, Minneapolis, MN 55455.
A variety of methods have been employed for deriving intermolecular structural parameters from observed rotational
constants of weakly bound complexes. Among these are methods that use formulas expressing the moments of inertia
of the complex in terms of intermolecular coordinates and the known moments of inertia of the free monomers. While
such formulas are available for a number of specific geometries, general forms have not been given. In this talk, equations
are presented for the inertial tensor components of a weakly bound complex in terms of intermolecular coordinates and
moments of inertia of the individual moieties. The result is a generalization of similar equations existing in the literature and
allows for the use of up to three angles to specify the orientation of an asymmetric rotor within a complex. The angles used
are well suited to treating the large amplitude motion characteristic of weakly bound systems and the resulting expressions
should be useful in the analysis of the rotational constants of weakly bound systems with complicated geometries.
237
WH03
SECOND MOMENTS (PLANAR MOMENTS) AND THEIR APPLICATION IN SPECTROSCOPY
15 min 1:59
ROBERT K. BOHN, Dept. of Chemistry, Univ. of Connecticut, Storrs, CT 06269-3060; JOHN A. MONTGOMERY, JR., H. HARVEY MICHELS, JASON N. BYRD, Dept. of Physics, Univ. of Connecticut, Storrs,
CT 06269-3046.
Second moments, also called planar moments (Pii = Σmi x2i ), are the spectroscopic parametersa used to determine substitution structures (rs ) ) by Kraitchman”s method from spectra of a molecule and its isotopologs. They are also useful for
discussing other molecular structural properties. Just as bond lengths and angles are considered transferable among similar
molecules, second moments of many common groups are also transferable. This paper discusses applications of second
moments of methylene/methyl groups, singly or multiply, isopropyl/tert-butyl groups, phenyl groups, perfluoro methylene/methyl groups, combinations of any of them, and planarity of molecules, the historically most common application
of second moments. The inertial defect is ∆ = (Ic − Ia − Ib ) or −2Pcc . Some authors err by assuming each isotopolog
provides three independent rotational constants, but in some cases they are not all independent.
a J.
Kraitchman, Am. J. Phys. 21 (17), 1953.
WH04
15 min 2:16
AN EMPIRICAL APPROACH TO OBTAINING ACCURATE MOLECULAR ROTATIONAL CONSTANTS FOR
ISOTOPICALLY-SUBSTITUTED SPECIES FROM AB INITIO CALCULATIONS
BRETT A. McGUIRE, P. BRANDON CARROLL, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125; GEOFFREY A. BLAKE, Division of Chemistry and
Chemical Engineering and Division of Geological and Planetary Sciences, California Institute of Technology,
Pasadena, CA 91125.
Recent advances in microwave spectroscopy, namely the development of broadband, chirped-pulse Fourier-transform microwave spectrometers, allow the acquisition of rotational spectra of isotopically-substituted species in natural abundance.
The characterization and assignment of these spectra is of particular interest as it applies to astrochemical observations of
such species in the interstellar medium. Here, we demonstrate an empirical method for determining rotational constants to
aid in the initial assignment of such spectra using a combination of laboratory data and ab initio calculations. The result is
an increase in the accuracy of these constants by as much as two orders of magnitude versus those resulting from simple
structure optimizations. We have applied this method to a variety of species including diatomic molecules (e.g. HCl), large
molecules with internal motion (e.g. CH3 COOH), ions (e.g. HCO+ ), clusters (e.g. H2 O·H2 O), and long carbon chain
molecules (e.g. HC7 N). We present the results of these analyses and comment on the applicability of this method to other
systems.
238
WH05
15 min 2:33
SINGULAR VALUE DECOMPOSITION-BASED MODELING OF TIME DOMAIN SIGNALS IN BROADBAND MICROWAVE SPECTROSCOPY
A singular value decomposition (SVD) signal processing method is newly
applied to molecular free induction decays (FIDs) obtained using a time
domain, broadband rotational spectrometer. It is demonstrated that for the
strongest spectral transitions the SVD method can determine transition frequencies with a precision matching that of the fast Fourier transform method.
Furthermore, the SVD-based analysis produces information concerning transition phase, amplitude, damping, and frequency for the strongest molecular
signals. These parameters are shown as useful in regards to time-domain
signal filtering. The computational expense of the SVD method is high and
therefore this approach has the disadvantage that with our present computers the full molecular FID must be considerably
truncated. The effects of FID truncation on the determined transition frequencies have been examined. Conversely, this
truncation method illustrates that broadband spectra may be recovered from fragments as small as 1 % of the complete FID.
The success of the SVD-based method is further examined in regards to weak signal detection, and frequency dependent
detection. The pure rotational spectrum of 1H,1H,2H-perfluorocyclobutane is used for illustrative purposes in this study.
WH06
15 min 2:50
PURE ROTATIONAL SPECTROSCOPY OF ASYMMETRIC TOPS IN THE UNDERGRADUATE CLASSROOM OR
LABORATORY
Due to concerns of complexity, the asymmetric top, for which κ =
(2B − A − C)/(A − C) 6= ± 1, is feared, or at least avoided, by many
instructors when explaining the rigid rotor. However, the spectral patterns formed by cold asymmetric rigid rotors in the centimeter-wave
region of the electromagnetic spectrum can be easily identified. We
will present some techniques for spectral analyses that we have successfully employed with undergraduate students who are either “prequantum mechanics" or are currently enrolled in a chemical quantum
mechanics class. The activities are simple, requiring the students to
first locate repeating patterns and then apply simple algebraic expressions in order to determine all three rotational constants. The method
will be illustrated using the spectra of 2,2,3,3-tetrafluoropropyl trifluoroacetate (CF3 C(=O)OCH2 CF2 CHF2 ), (E)-1,3,3,3-tetrafluoropropene (CF3 CH=CHF), 1H,1H,2H-perfluorocyclobutane
(CF2 CF2 CHFCH2 ), and 2H-nonafluorobutane (CF3 CHFCF2 CF3 ). The first two of these species have predominantly atype spectra, the third has a predominantly b-type spectrum, the fourth has a predominantly c-type spectrum.
239
WH07
15 min 3:07
A NEW E-BAND (60 - 90 GHz) FOURIER TRANSFORM MILLIMETER-WAVE SPECTROMETER
An E-band (60 - 90 GHz) cavity Fourier transform millimeter-wave (FTmmW) spectrometer system has been built and
used for molecular measurements for the first time. These frequencies are the highest acheived using cavity FTM/mmW
techniques. This new system, implemented as a millimeter frequency band on the current FTMW spectrometer of the
Ziurys group, utilizes waveguide for radiation propagation and commercial E-band doublers and quadruplers to achieve
continuous operation from 60 to 90 GHz. This system also employs an ALMA Band 2 low-noise amplifier (LNA), designed
by NRAO. The Fabry-Perot cavity consists of two 170 mm diameter mirrors with a radius of curvature of 840 mm and a
separation of 700 mm. The Q factor of the system is around 100,000. Using this system, the NKa,Kc = 404 → 303 transition
of ScC2 near 62 GHz has been recorded for the first time. These data, as well as other molecular lines, will be presented.
WH08
15 min 3:24
THE FOURIER TRANSFORM MICROWAVE/MILLIMETER SPECTRUM OF ScO (X Σ )
2
+
D. T. HALFEN, J. MIN, and L. M. ZIURYS, Department of Chemistry, Department of Astronomy, and Steward Observatory, University of Arizona, Tucson, AZ 85721.
The pure rotational spectra of ScO (X2 Σ+ ) have been recorded in the 4 - 90 GHz range using Fourier transform microwave/millimeter (FTM/mmW) techniques. This species was created in a supersonic jet expansion of laser-ablated
scandium vapor and N2 O gas, diluted in argon. The N = 1 → 0 and 2 → 1 rotational transitions in both v = 0 and 1
have been measured near 30 and 61 GHz, respectively. The data over 60 GHz were obtained using a new E-band (60 - 90
GHz) FTmmW spectrometer system. The data have been analyzed, and rotational, fine, and hyperfine constants have been
determined, which are in good agreement with those from past optical studies. ScO is a potential circumstellar molecule
in giant/supergiant stars, where it is produced in oxygen-burning nucleosynthesis.
Intermission
WH09
15 min 4:00
SUBMILLIMETER SPECTROSCOPIC DIAGNOSTICS IN A SEMICONDUCTOR PROCESSING PLASMA
YASER H. HELAL, CHRISTOPHER F. NEESE, JENNIFER A. HOLT, FRANK C. DE LUCIA, Department
of Physics, The Ohio State University, Columbus, OH 43210; PAUL R. EWING, Applied Materials, Austin,
TX 78724; PHILLIP J. STOUT, MICHAEL D. ARMACOST, Applied Materials, Sunnyvale, CA 94085.
Millimeter and submillimeter rotational spectroscopy was used to characterize and measure the abundances of compounds
in a semiconductor processing plasma. Plasmas were generated using flow mixtures of Ar, C4 F8 , and O2 in a chamber with
quartz windows for submillimeter wave transmission. Species of interest included the plasma products CF, CF2 , COF2 ,
and CO. Abundances as a function of flow mixtures and pressures as well as rf drive levels will be presented.
240
WH10
15 min 4:17
IR/THZ DOUBLE RESONANCE SPECTROSCOPY APPROACH FOR REMOTE CHEMICAL DETECTION AT ATMOSPHERIC PRESSURE
ELIZABETH A. TANNER and DANE J. PHILLIPS, IERUS Technologies, 2904 Westcorp Blvd Ste 210,
Huntsville, AL 35805; FRANK C. DE LUCIA, Department of Physics, 191 Woodruff Ave. Ohio State University, Columbus, OH 43210; HENRY O. EVERITT, Army Aviation and Missile RD&E Center, Redstone
Arsenal, AL 35898.
A remote sensing methodology based on infrared/terahertz (IR/THz) double resonance (DR) spectroscopy is shown to
overcome limitations traditionally associated with either IR or THz spectroscopic approaches for detecting trace gases in
an atmosphere. The applicability of IR/THz DR spectroscopy is explored by estimating the IR and THz power requirements
for detecting a 100 part-per-million-meter cloud of methyl fluoride, methyl chloride, or methyl bromide at ranges up to 1km
in three atmospheric windows below 0.3 THz. These prototypical molecules are used to ascertain the dependence of the
DR signal-to-noise ratio on IR and THz beam power. A line-tunable CO2 laser with 100 ps pulse duration generates a DR
signature in four rotational transitions on a time scale commensurate with collisional relaxations caused by atmospheric N2
and O2 . A continuous wave THz beam is frequency tuned to probe one of these rotational transitions so that laser-induced
absorption variations in the analyte cloud are detected as temporal power fluctuations synchronized with the laser pulses. A
combination of molecule-specific physics and scenario-dependent atmospheric conditions are used to predict the signal-tonoise ratio (SNR) for detecting an analyte as a function of cloud column density. A methodology is presented by which the
optimal IR/THz pump/probe frequencies are identified. These estimates show the potential for low concentration chemical
detection in a challenging atmospheric scenario with currently available or near term hardware components.
WH11
15 min 4:34
A MICRO-CANTILEVER BASED PHOTOACOUSTIC DETECTOR OF TERAHERTZ RADIATION FOR CHEMICAL
SENSING
NATHAN E. GLAUVITZ, RONALD A. COUTU JR., Department of Electrical and Computer Engineering, Air Force Institute of Technology, 2950 Hobson Way, Wright-Patterson AFB, OH 45433, USA;
MICHAEL N. KISTLER, RYAN F. HAMILTON, DOUGLAS T. PETKIE, IVAN R. MEDVEDEV, Department of Physics, Wright State University, 3640 Colonel Glenn Highway, Dayton, OH 45435, USA.
In this paper we describe a novel photoacoustic detector that can detect radiation in the Terahertz/sub-millimeter
(THz/smm) spectral range, is immune to the effect of standing waves, and potentially can have spectral response that is
independent of the absorption path length, thus offering crucial advantages for acquisition of THz/smm molecular spectra.
The photoacoustic effect occurs when the energy from electromagnetic waves is absorbed by molecules and collisionally
transferred into translational energy, thus resulting in local heating induced by the radiation. If radiation produced by the
source is modulated, an acoustic wave results which can be detected by a pressure sensitive device such as a microphone
or a cantilever. This transduction of the THz signal into a photoacoustic wave is what makes this approach insensitive
to the detrimental standing waves associated with traditional THz sensors and allows for a significant reduction in the
size of the absorption cell. A Microelectromechanical system (MEMS) cantilever pressure sensor was designed, modeled,
fabricated, and tested for sensing the photoacoustic response of gases to THz/smm radiation. Here we present our manufacturing, experimental set-up and most recent spectroscopic results, which demonstrate the capabilities of this spectroscopic
technique.
241
WH12
15 min 4:51
A TWO-COLOR FOURIER TRANSFORM MM-WAVE SPECTROMETER FOR GAS ANALYSIS OPERATING FROM
260-295 GHZ
AMANDA L. STEBER, BRENT J. HARRIS , KEVIN K. LEHMANN, and BROOKS H. PATE, Department
We have designed a two-color mm-wave spectrometer for Fourier transform mm-wave spectroscopy that uses consumer
level components for the tunable synthesizers, digital control of the pulse modulators, and digitization of the coherent free
induction decay (FID). The excitation pulses are generated using an x24 active multiplier chain (AMC) that produces a
peak power of 30 mW. The microwave input to the AMC is generated in a frequency up conversion circuit that accepts a
microwave input frequency from about 2-4 GHz. This circuit also generates the input to the mm-wave subhamonic mixer
that creates the local oscillator from a separate 2-4 GHz microwave input. Excitation pulses at two independently tunable
frequencies are generated using a dual-channel source based on a low-cost, wideband synthesizer integrated circuit (Valon
Technology Model 5008). The outputs of the synthesizer are pulse modulated using a PIN diode switch that is driven using
the arbitrary waveform generator (AWG) output of a USB-controlled high-speed digitizer / arbitrary waveform generator
combination unit (Tie Pie HS-5 530 XM). The two pulses are combined using a Wilkinson power divider before input to
the up conversion circuit. The FID frequency is down converted in a two-stage mixing process to 65 MHz. The two LO
frequencies used in the receiver are provided by a second Valon 5008. The FID is digitized at 200 MSamples/s using the
12-bit Tie Pie digitizer. The digital oscilloscope (and its AWG channel) and the two synthesizers use a 10 MHz reference
signal from a Rubidium clock to permit time-domain signal averaging. A key feature of the digital oscilloscope is its deep
memory of 32 Mpts (complemented by the 64 Mpt memory in the 240 MS/s AWG). This makes it possible to perform
several one- and two-color coherent measurements, including pulse echoes and double-resonance spectroscopy, in a single
readout experiment to speed the analysis of mm-wave rotational spectra. The spectrometer sensitivity and frequency
accuracy are illustrated by high-speed measurements of OCS rotational transitions for low-abundance isotopes. Examples
of pulse echo measurements to determine the collisional relaxation rate and two-color double-resonance measurements to
confirm the presence of a molecular species will be illustrated using OCS as the room-temperature gas sample.
WH13
GAS ANALYSIS BY FOURIER TRANSFORM MM-WAVE SPECTROSCOPY
15 min 5:08
BRENT J. HARRIS, AMANDA L. STEBER, KEVIN K. LEHMANN, and BROOKS H. PATE, Department
Molecular rotational spectroscopy of low pressure, room temperature gases offers high chemical selectivity and sensitivity with the potential for a wide range of applications in gas analysis. A strength of the technique is the potential to
identify molecules that have not been previously studied by rotational spectroscopy by comparing experimental results to
predictions of the spectroscopic parameters from quantum chemistry so called library-free detection. The development
of Fourier transform mm-wave spectrometers using high peak power (30 mW) active multiplier chain mm-wave sources
brings new measurement capabilities to the analysis of complex gas mixtures. Strategies for gas analysis based on highthroughput mm-wave spectroscopy and arbitrary waveform generator driven mm-wave sources are described. Several new
measurement capabilities come from the intrinsic time-domain measurement technique. High-sensitivity double-resonance
measurements can be performed to speed the analysis of a complex gas sample containing several species. This technique
uses a pi-pulse to selectively invert the population of two selected rotational energy levels and the effect of this excitation
pulse on all other transitions in the spectrometer operating range is monitored using segmented chirped-pulse Fourier transform spectroscopy. This method can lead to automated determination of the molecular rotational constants. Rapid pulse
duration scan experiments can be used to estimate the magnitude and direction of the dipole moment of the molecule from
an unknown spectrum. Coherent pulse echo experiments, using the traditional Hahn sequence or two-color population recovery methods, can be used to determine the collisional relaxation rate of the unknown molecule. This rate determination
improves the ability to estimate the mass of the unknown molecule from the determination of the Doppler dephasing rate.
By performing a suite of automated, high-throughput measurements, there is the potential to determine the shape (via the
rotational constant), electric properties (the dipole moments and its direction in the principal axis system), and the mass of
the molecule to aid its identification.
242
WH14
15 min 5:25
A SEGMENTED CHIRPED-PULSE FOURIER TRANSFORM MM-WAVE SPECTROMETER (260-295 GHZ) WITH
REAL-TIME SIGNAL AVERAGING CAPABILITY
BRENT J.HARRIS, AMANDA L. STEBER, and BROOKS H. PATE, Department of Chemistry, University
of Virginia, Charlottesville, VA 22904.
The design and performance of a 260-295 GHz segmented chirped-pulse Fourier transform mm-wave spectrometer is
presented. The spectrometer uses an arbitrary waveform generator to create an excitation and detection waveform. The excitation waveform is a series of chirped pulses with 720 MHz bandwidth at mm-wave and about 200 ns pulse duration. The
excitation pulses are produced using an x24 active multiplier chain with a peak power of 30 mW. Following a chirped pulse
excitation, the molecular emission from all transitions in the excitation bandwidth is detected using heterodyne detection.
The free induction decay (FID) is collected for about 1.5 microseconds and each segment measurement time period is 2
microseconds. The local oscillator for the detection in each segment is also created from the arbitrary waveform generator. The full excitation waveform contains 50 segments that scan the chirped pulse frequency and LO frequency across
the 260-295 GHz frequency range in a total measurement time of 100 microseconds. The FID from each measurement
segment is digitized at 4 GSamples/s, for a record length of 400 kpts. Signal averaging is performed by accumulating the
FID signals from each sweep through the spectrum in a 32-bit FPGA. This allows the acquisition of 16 million sequential
260-295 GHz spectra in real time. The final spectrum is produced from fast Fourier transform of the FID in each measurement segment with the frequency calculated using the segment’s LO frequency. The agility of the arbitrary waveform
generator light source makes it possible to perform several coherent spectroscopic measurements to speed the analysis of
the spectrum. In particular, high-sensitivity double-resonance measurements can be performed by applying a pi-pulse to
a selected molecular transition and observing the changes to all other transitions in the 260-295 GHz frequency range of
the spectrometer. In this mode of operation, up to 50 double-resonance frequencies can be used in each segment with the
double-resonance signal collection taking place in real time.
WH15
15 min 5:42
COHERENT SYNCHROTRON RADIATION FOR ROTATIONAL SPECTROSCOPY: APPLICATION TO THE ROTATIONAL SPECTRUM OF PROPYNAL IN THE 200-750 GHz RANGE
J. BARROS, P. ROY, Synchrotron SOLEIL, L’Orme des Merisiers Saint-Aubin, 91192 Gif-sur-Yvette, France;
D. APPADOO, D. Mc NAUGHTON, Australian Synchrotron Light Source, 800 Blackburn Road Victroria
3168 and Monash University, School of Chemistry, Clayton, Victoria 3800 Australia.; E. ROBERTSON, La
Trobe University, Department of Chemistry, Victoria, 3086, Australia; L. MANCERON, Laboratoire LADIR,
CNRS, Université Pierre et Marie Curie, 75252 Paris Cedex, France.
In storage rings, short electron bunches can produce an intense THz radiation called Coherent Synchrotron Radiation
(CSR). The flux of this emission between 250 and 750 GHz (in the mW range, up the 10000 times the regular synchrotron
emission) is very advantageous for broad band absorption spectroscopy, using interferometric techniques. This source
is, however, inherently difficult to stabilize, and intensity fluctuations lead to artifacts on the FT-based measurements,
which strongly limit the use of CSR in particular for high-resolution measurements. At SOLEIL however, by screening
different currents and bunch lengths, we defined stable CSR conditions for which the signal-to-noise ratio (S/N) allows for
measurements at high resolution. Moreover, we developed an artifact correction system, based on a simultaneous detection
of the input and the output signals of the interferometer, which allows to further improve the S/N. For this purpose, the
optics and electronics of two bolometers were matched. The stable CSR combined with this ingenious technique allowed
us to record for the first time high-resolution FT spectra in the sub-THz range, with a S/N of 100 in a few hours. This
enables many applications such as broadband rotational spectra in the THz range, studies of molecules with low frequency
torsional modes, absolute intensities determinations, or studies of unstable species. Results obtained on Propynal illustrate
these possibilities and enabled to improve significantly the ground state spectroscopic constants.
243
WH16
DEVELOPMENT OF A REDUCED-COST CHIRPED PULSE MICROWAVE SPECTROMETER
15 min 5:59
IAN A. FINNERAN, DANIEL B. HOLLAND, P. BRANDON CARROLL, Department of Chemistry, California Institute of Technology, Pasadena, CA 91125; and GEOFFREY A. BLAKE, Divisions of Geological
& Planetary Sciences and Chemistry & Chemical Engineering, California Institute of Technology, Pasadena,
CA 91125.
Chirped pulse Fourier transform microwave (CP-FTMW) spectroscopy has become a ubiquitous technique in the highresolution molecular spectroscopy community. Unfortunately, many components of CP-FTMW spectrometers are extremely expensive. Here we report of the development of an inexpensive microwave circuit and we present spectra of
tetrahydrofuran and methanol collected between 8-16 GHz. Possible applications in remote sensing will also be discussed.
244
WI. INFRARED/RAMAN
Chair: REBECCA PEEBLES, Eastern Illinois University, Charleston, IL
WI01
15 min 1:30
INFRARED SPECTROSCOPIC INVESTIGATION ON HIGH ACIDITY OF DIETHYLETHER CATION
TOMOYA ENDO,YOSHIYUKI MATSUDA,ASUKA FUJII, Depertment of Chemistry, Graduate School of
Science,Tohoku University, Sendi 980-8578, Japan; KAITO TAKAHASHI, Institute of Atomic and Molecular
Sciences, Academia Sinca,Taipei 10617, Taiwan.
We performed infrared spectroscopy of a diethylether cation which was generated by the vacuum-ultraviolet photoionization. In the observed spectrum, the stretch vibration of the CH bond next to the oxygen atom appears with high intensity in
the lower frequency region than ordinary alkyl CH stretches. Comparison of infrared spectroscopic results and theoretical
calculations reveals that the low frequency of the CH stretch originates from hyperconjugation between the CH bonding
orbital and the nonbonding orbital of the oxygen atom. This hyperconjugation also induces the increase of the acidity of
the CH bond as well as its stretch band intensity.
WI02
15 min 1:47
STRUCTURAL, CONFORMATIONAL AND VIBRATIONAL STUDIES OF ISOCYANOCYCLOPENTANE FROM
INFRARED, RAMAN SPECTRA AND AB INITIO CALCULATIONS
DATTATRAY K. SAWANT, JOSHUA J. KlAASSEN, JAMES R. DURIG, DEPARTMENT OF CHEMISTRY,
UNIVERSITY OF MISSOURI-KANSAS CITY, MO 64110 USA.
The infrared and Raman spectra (3200 to 50 cm−1 ) of the gas, liquid or solution, and solid have been recorded of isocyanocyclopentane, c -C5 H9 NC. FT-microwave studies have also been carried out and 23 transitions were recorded for the
envelope-axial (Ax) conformer. Variable temperature (-55 to -100◦ C) studies of the infrared spectra (3200 to 400 cm−1 )
dissolved in liquid xenon have been carried out. From these data, both the Ax and envelope-equatorial (Eq) conformers
have been identified and their relative stabilities obtained. The enthalpy difference has been determined to be 102 ±10cm−1
(1.21 ±0.03kJmol−1) with the Ax conformer the more stable form. The percentage of the Eq conformer is estimated to
be 38 ± 1% at ambient temperature. The conformational stabilities have been predicted from ab initio calculations by
utilizing several different basis sets up to aug-cc-pVTZ from both MP2(full) and density functional theory calculations
by the B3LYP method. Vibrational assignments have been made for the observed bands for both conformers with initial
predictions by MP2(full)/6-31G(d) ab initio calculations to obtain harmonic force constants, wavenumbers, infrared intensities, Raman activities and depolarization ratios for both conformers. The heavy atom distances (): C≡N = 1.176 ;
C-N≡C= 1.432; C-Cβ ,Cβ ′ = 1.534; Cβ -Cγ , Cγ ′ = 1.542; Cγ -Cγ ′ = 1.554 and angles (◦ ):∠C-N= 177.8; ∠Cβ C-N= 110.4;
∠Cβ CCβ ′ = 102.9; ∠CCβ Cγ = 103.6; ∠Cβ Cγ Cγ ′ = 105.9. The results are discussed and compared to the corresponding
properties of some related molecules.
245
WI03
15 min 2:04
MICROWAVE AND INFRARED SPECTRA, ADJUSTED R0 STRUCTURAL PARAMETERS, CONFORMATIONAL
STABILITIES, VIBRATIONAL ASSIGNMENTS, AND AB INITIO CALCULATIONS OF CYCLOBUTYLCARBOXYLIC ACID CHLORIDE
JOSHUA J. KLAASSEN, PETER GRONER, JAMES R. DURIG, Department of Chemistry, University of
Missouri-Kansas City, Kansas City, MO 64110 USA.
The FT-microwave spectrum of cyclobutylcarboxylic acid chloride, c-C4 H7 C(O)Cl, has been recorded and 153 transitions
for the 35 Cl and 37 Cl isotopologues have been assigned for the gauche-equatorial conformation. The ground state rotational constants were determined from these assignments with following values for 35 Cl [37 Cl]: A = 4349.84294(48)
[4322.0555(56)], B = 1414.80319(36) [1384.50581(105)], C = 1148.24114(18) [1126.35465(101)]. From the determined
microwave rotational constants and ab initio MP2(full)/6-311+G(d,p) predicted structural values, adjusted r0 parameters
are reported. Variable temperature (-70 to -100o C) infrared spectra (4000 to 400 cm−1 ) were recorded in liquid xenon and
gauche-equatorial conformer is the most stable form with an enthalpy differences of 91 ± 9 cm−1 (1.09 ± 0.05 kJ/mol)
with gauche-axial and 173 ± 17 cm−1 (2.07 ± 0.04 kJ/mol) with the trans-equatorial conformer. The relative amounts
present at an ambient temperature are 54% gauche-equatorial, 35 ± 1% gauche-axial and 12 ± 1% trans-equatorial. The
conformational stabilities have been predicted from ab initio calculations utilizing several different basis sets up to augcc-pVTZ from both MP2(full) and density functional theory calculations by the B3LYP method. Vibrational assignments
have been provided for the observed bands for all three conformers which are supported by ab initio calculations to predict
harmonic force constants, vibrational wavenumbers, infrared intensities, Raman activities and depolarization ratios. The
results are discussed and compared to the corresponding properties of some related molecules.
WI04
15 min 2:21
LOWERING OF KETO-ENOL TAUTOMERIZATION BARRIER OF CYCLIC DIKETONES VIA CH· · · O INTERACTION
T. CHAKRABORTY, B. BANDYOPADHYAY, P. BANERJEE and P. PANDEY, Department of Physical
Chemistry, Indian Association for the cultivation of science, Calcutta 700032, India. E-mail: [email protected].
Molecular association and keto-enol tautomerization of β-cyclohexanedione (β-CHD) and analogues have been investigated in argon matrix and also in a thin solid film prepared by depositing pure β-CHD vapour on a cold (8 K) KBr window.
Infrared spectra reveal that in low-pressure vapour and argon matrix, the molecules are exclusively in diketo tautomeric
form. The CH· · · O hydrogen bonded dimers of the diketo tautomer are produced by annealing the matrix at 28 K. No
indication is found for keto-enol tautomerization of β-CHD in dimeric complexes in argon matrix within the temperature
range of 8-28 K. On the other hand, in the thin film of pure diketo tautomer, the conversion initiates when the film is
heated at temperatures above 165 K. The observed threshold appears to be associated with excitation of the intermolecular modes in the solid, and the IR spectra recorded at high temperatures display narrowing of vibrational bandwidths,
which has been associated to re-orientations of the molecules in solid. The non-occurrence of tautomerization in the dimer
is consistent with the prediction of electronic structure calculations at B3LYP/6-311++G**, M05-2X/6-311++G** and
MP2/6-311++G** levels. The transition state calculation predicts that CH· · · O interaction has a dramatic effect on lowering of the tautomerization barrier, from more than 60 kcal/mol of bare molecule to ∼35-40 kcal/mol in dimers. Details of
the results on analogous systems will be discussed in the talk.
Reference
“CH· · · O Interaction Lowers Hydrogen Transfer Barrier to Keto-Enol Tautomerization of β-Cyclohexanedione: Combined
Infrared Spectroscopic and Electronic Structure Calculation Study", B. Bandyopadhyay, P. Pandey, P. Banerjee, A. K.
Samanta, and T. Chakraborty, J. Phys. Chem A. 116,3836-3845 (2012).
246
WI05
15 min 2:38
A SPECTROSCOPIC AND THEORETICAL STUDY OF WEAK INTRAMOLECULAR OH· · · π INTERACTIONS IN
ALLYL CARBINOL AND METHALLYL CARBINOL
SIDSEL D. SCHROEDER, KASPER MACKEPRANG, HENRIK G. KJAERGAARD, Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen .
The weak intramolecular OH· · · π interactions in allyl carbinol and methallyl carbinol have been studied using a combination of NIR spectroscopy and theory. The third OH-stretching overtone region of vapor phase allyl carbinol and methallyl
carbinol have been recorded with intracavity laser photoacoustic spectroscopy to study the effect of an enhanced OH· · · π
interaction in methallyl carbinol arising from the electron donating methyl group. Local mode calculations were employed
to assign the observed bands. The OH-stretching transition frequency of methallyl carbinol was observed to be red shifted
relative to the OH-stretching transition frequency of allyl carbinol. A red shift of the transition frequency is in this context normally interpreted as a signature of hydrogen bonding. Whether the OH· · · π interaction can be categorized as a
hydrogen bond will be discussed in this talk.
Intermission
WI06
VIBRATIONAL SPECTROSCOPIC INVESTIGATION AND CONFORMATIONAL
HEPTYLAMINE: A COMPARATIVE DENSITY FUNCTIONAL STUDY
10 min 3:15
ANALYSIS OF 1-
MAHIR TURSUN, Department of Physics, Dumlupinar University, Kutahya, 43100, Turkey; and GURKAN
KESAN, Institute of Physics and Biophysics, Faculty of Science, University of South Bohemia, Branisovská
31, Ceské Budéjovice, 370 05, Czech Republic; and CEMAL PARLAK, Department of Physics, Dumlupinar
University, Kutahya, 43100, Turkey; MUSTAFA SENYEL, Science Faculty, Department of Physics, Anadolu
University, Eskisehir, Turkey 26470.
FT-IR and Raman spectra of 1-heptylamine (1-ha) were experimentally reported in the region of 4000-10 cm-1 and 4000100 cm-1, respectively. The conformational analysis, optimized geometric parameters, normal mode frequencies and corresponding vibrational assignments of 1-ha (C7H17N) were theoretically examined by means of Becke-3-Lee-Yang-Parr
(B3-LYP) density functional theory (DFT) method together with 6-31++G(d,p) basis set. Furthermore, reliable vibrational
assignments were made on the basis of potential energy distribution (PED) calculated and the thermodynamics functions,
highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) of 1-ha were predicted. Calculations
were carried out with the possible ten conformational isomers (TT, TG, GT, GT1, GG1, GG2, GG3, GG4, GG5, GG6;
T and G denote trans and gauge) of 1-ha, both in gas phase and in solution. Solvent effects were investigated using benzene and methanol. All results indicates that B3-LYP method provides satisfactory results for the prediction vibrational
wavenumbers, TT isomer is the most stable form of 1-ha and the conformational energy barrier is independent of the
solvent whereas the vibrational frequencies and assignments, IR and Raman intensities of 1-ha are solvent dependent.
247
WI07
15 min 3:27
LOWEST ENERGY VIBRATIONAL MODES OF NINE NAPHTHALENE DERIVATIVES; EXPERIMENT AND THEORY
M. A. MARTIN-DRUMELa , O. PIRALI, Y. LAQUAISb , Institut des Sciences Moléculaires d’Orsay, CNRS,
UMR 8214, Université Paris XI, bât. 210, 91405 Orsay Cedex, France; SOLEIL Synchrotron, AILES
beamline, L’orme des Merisiers, Saint-Aubin, 91192 Gif-Sur-Yvette, France; C. FALVO, P. PARNEIX and
PH. BRECHIGNAC, Institut des Sciences Moléculaires d’Orsay, CNRS, UMR 8214, Université Paris XI, bât.
210, 91405 Orsay Cedex, France.
FIR gas phase absorption spectra of nine naphthalene
derivatives (azulene, quinoline, isoquinoline, biphenyl,
diphenylmethane, bibenzyl, 2-, 3-, and 4-phenyltoluene)
have been recorded at medium resolution (0.5 cm−1 ) using a Fourier transform Bruker IFS125 interferometer located on the AILES beamline of SOLEIL synchrotron.
Assignments of these weak vibrational bands were performed using density-functional theory calculations carried out at the harmonic and anharmonic levels (B971/6-311G(d,p)). Molecular structure dependence of the
FIR spectra is discussed based on the comparative study
of several selected FIR modes.
a Present
b Present
Quinoline
(C9 H7 N)
Biphenyl
(C12 H10 )
2-phenyltoluene
(C13 H12 )
Diphenylmethane
(C13 H12 )
3-phenyltoluene
(C13 H12 )
Bibenzyl
(C14 H14 )
4-phenyltoluene
(C13 H12 )
N
Isoquinoline
(C9 H7 N)
N
Azulene
(C10 H8 )
address: LPCA, EA 4493, Université du Littoral Côte d’Opale, 59140 Dunkerque, France
address: CEA, IRAMIS, SPAM, Lab. Francis Perrin, 91192 Gif-sur-Yvette, France
WI08
10 min 3:44
TOWARD COMPUTATIONAL SPECTROSCOPY STUDIES FOR LARGE MOLECULAR SYSTEMS
Integrated computational approaches built on quantum mechanical (QM) methods
combined with time-independent schemes to account for nuclear motion effects
are applied to the spectroscopic investigation of molecular systems, from large
biomolecules to hybrid supra-molecular systems. Within the time-independent
approaches, vibrational spectra are computed including anharmonicities through
perturbative corrections while UV-vis line-shapes are simulated accounting for
the vibrational structure; in both cases, the environmental effects are taken into
account by explicit or continuum models. Extension to larger systems relies on
reduced dimensionality approaches and effective schemes to select transitions of
interest, available for both vibrational and vibronic spectra. Such procedures are
exploited to simulate IR and UV-vis spectra leading in all cases to good agreement
with experimental observations and allowing to dissect different effects underlying
spectral phenomena, finally, paving a feasible route toward the state-of-the-art computational spectroscopy studies, even
for relatively large molecular systems [1,2].
1. V. Barone, A. Baiardi, M. Biczysko, J. Bloino, C. Cappelli, F. Lipparini Phys. Chem. Chem. Phys, 14, 12404, 2012
2. V. Barone, M. Biczysko, J. Bloino, M. Borkowska-Panek, I. Carnimeo, P. Panek, Int. J. Quantum Chem. 112, 2185,
2012
248
WI09
15 min 3:56
DETERMINATION
OF
STRUCTURAL
AND
VIBRATIONAL
PROPERTIES
OF
5QUINOLINECARBOXALDEHYDE USING EXPERIMENTAL FT-IR, FT-RAMAN TECHNIQUES AND THEORETICAL HF AND DFT METHODS
MUSTAFA KUMRU, MUSTAFA KOCADEMIR, TAYYIBE BARDAKCI, Department of Physics, Faculty
of Arts and Sciences, Fatih University, 34500 Buyukcekmece, Istanbul, Turkey.
Quinoline derivatives have been used in several pharmaceuticals. They have vital roles in regulating the functions of
DNA and cancerous cells. It’s necessary to determine the structures and spectroscopic properties of quinoline derivates.
In this study, the FT-IR (including mid and far regions) and FT-Raman spectra of 5-quinolinecarboxaldehyde have
been investigated. Hartree-Fock (HF) and density functional B3LYP calculations have also been employed with the 6311++G(d,p) basis set for investigating the structural and spectroscopic properties of the cis and trans conformers of 5quinolinecarboxaldehyde. Experimental and theoretical results have been compared and the results are in good agreement
with each other.
Keywords: 5-quinolinecarboxaldehyde; Vibrational Spectroscopy; FT-IR spectra; FT-Raman spectra; Vibrational Modes;
HF; DFT
[1] V. Kucuk, A. Altun, M. Kumru, Spectrochim. Acta Part A 85(2012)92–98
[2] M. Kumru, V. Kucuk, T. Bardakci, Spectrochim. Acta Part A 90(2012)28–34
[3] M. Kumru, V. Kucuk, M. Kocademir, Spectrochim. Acta Part A, 96 (2012) 242–251
We thank the Turkish Scientific and Technical Research Council (TUBITAK) for their financial support through National
Postdoctoral Research Scholarship Programme and Scientific Research Fund of Fatih University under the project number
P50011001 G (1457).
WI10
15 min 4:13
CYCLIC CONSTRAINTS ON CONFORMATIONAL FLEXIBILITY IN γ-PEPTIDES: CONFORMATION-SPECIFIC
IR AND UV SPECTROSCOPY
PATRICK S. WALSH, RYOJI KUSAKA and TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette. IN 47907; BRIAN F. FISHER and SAMUEL H. GELLMAN, Department of Chemistry, University of Wisconsin-Madison, Madison, WI 53706.
Spectroscopic studies of flexible peptides in the gas phase can provide insight to their inherent structural preferences in
the absence of solvent. Recently, there has been increased attention paid to synthetic foldamers containing non-natural
residues that can be specifically engineered to robustly form particular secondary structures. These engineered peptides
have potential in therapeutic drug design because they are resistant to enzymatic degradation. Specifically, the Gellman
group has synthesized a γ-peptide with a six membered cyclic constraint in the γ 4 -γ 3 position and an ethyl group at
the γ 2 position (γ ACHC ). The three stereocenters have a well-defined chirality [S,S,S]. These two features constrain the
relative orientation of adjacent amide groups, thereby favoring a particular "pitch" to the turn. Solution phase results
indicate that constrained γ-peptides induce the formation of a 14-helix.a Ac-γACHC -NHBz, its monohydrate and AcγACHC -γACHC -NHBz have been studied using ultraviolet (UV) and infrared (IR) double-resonance methods to obtain
conformation-specific spectra under jet-cooled conditions in the gas phase. IR spectra in the hydride stretch (3300-3750
cm−1 ), amide I/II and OH bend (1400-1800 cm−1 ) were recorded and compared to predictions using density functional
methods (DFT) and harmonic frequency calculations. We will compare the present results on constrained γ-peptides with
corresponding results on unconstrained analogs. Data obtained for the monohydrated water cluster of Ac-γACHC -NHBz
will also be presented, including assignment of the water bend fundamental, which appears in the midst of transitions due
to the amide II vibrations.
a L.
Guo, W. Zhang, A. G. Reidenbach, M. W. Giuliano, I. A. Guzei, L. C. Spencer and S. H. Gellman Angew. Chem. Int. Ed. 2011, 50, 5843-5846
249
WI11
15 min 4:30
CONFORMATION-SPECIFIC UV and IR SPECTROSCOPY OF CONFORMATIONALLY CONSTRAINED α/γ PEPTIDE FOLDAMERS
RYOJI KUSAKA, Department of Chemistry, Purdue University, West Lafayette, IN 47907, and Department of Chemistry, Graduate School of Science, Hiroshima University, Higashi-Hiroshima, 739-8526, Japan;
DI ZHANG, PATRICK WALSH, JOSEPH GORD, and TIMOTHY S. ZWIER, Department of Chemistry,
Purdue University, West Lafayette, IN 47907; BRIAN F. FISHER, and SAMUEL H. GELLMAN, Department
of Chemistry, University of Wisconsin, Madison, WI 53706.
Synthetic foldamers composed of heterogeneous backbones offer constructs for building unique secondary structures.
α/γ-peptides juxtapose the α-amino acid sub-units typical of proteins with γ-amino sub-units. Gellman and co-workers
have developed efficient syntheses of α/γ-peptides that incorporate a cyclohexyl ring constraint at the γ 3 -γ 4 bond to limit
backbone torsional mobility, and found that they form helices held together by C=O(i)···H-N(i+3) H-bonds composing
12-membered rings both in solution and in crystalline form. a This talk will present a detailed study of the singleconformation double-resonance UV and IR spectroscopy of Ac-Ala-γ ACHC -NH-benzyl (αγ) and Ac-γ ACHC -Ala-NHbenzyl (γα) capped peptides, in which γ ACHC residues are constrained by a cis cyclohexyl ring at γ 3 -γ 4 bond with an
ethyl group at γ 2 position. The two αγ and γα peptides have three amide groups that are the minimum length necessary
to form a 12-membered H-bond. Conformational assignments were made using the NH stretch, C=O stretch (amide I),
and NH bend (amide II) regions of the IR spectrum with the aid of DFT calculations. The double-resonance UV and
IR spectroscopy uncovered the presence of 6 conformers for αγ and 4 conformers for γα. In the two peptides, three of
ten structures incorporate bifurcated double rings made of 12-membered C=O(1)···H-N(3) ring, which is the first stage
of the 12-helix, and 7- or 9-membered C=O(1)···H-N(2) ring via nearest-neighbor interaction. The other seven structures
are constructed based on 5-, 7-, and 9-membered nearest-neighbor H-bonds. The similarities and differences between
structures observed for the two two αγ and γα peptides will be discussed.
a L.
Guo, Y. G. Chi, A. M. Almeida, I. A. Guzei, B. K. Parker, and S. H. Gellman, J Am Chem Soc, 2009, 131, 16018-16020.
WI12
15 min 4:47
MIXED CYCLIC CONSTRAINTS ON CONFORMATIONAL FLEXIBILITY IN β/γ-PEPTIDES: CONFORMATION
SPECIFIC IR AND UV SPECTROSCOPY
JOSEPH R. GORD, PATRICK S. WALSH, and TIMOTHY S. ZWIER, Department of Chemistry, Purdue
University, West Lafayette. IN 47907; BRIAN F. FISHER and SAMUEL H. GELLMAN, Department of
Chemistry, University of Wisconsin-Madison, Madison, WI 53706.
In order to further understand the intramolecular forces governing secondary structure formation in peptides and to provide
benchmarks for the computational community, conformation-specific spectroscopy techniques have been applied to several
model systems provided by Dr. Sam Gellman’s research group at the University of Wisconsin-Madison. In the present
work, two model β/γ-peptides, Ac-β ACP C -γ ACHC -NHBz and Ac-γ ACHC -β ACP C -NHBz have been investigated using
single and double resonance ultraviolet and infrared spectroscopy to elucidate their intrinsic folding propensities. The
β-peptide is constrained by a five-membered ring spanning the β 3 -β 2 positions (β ACP C ) and the γ-peptide is constrained
by a six-membered ring spanning the γ 4 -γ 3 positions with an additional ethyl group at γ 2 (γ ACHC ). Resonant twophoton ionization (R2PI) spectra from 37250 to 37750 cm−1 were obtained and subsequently interrogated using UV-UV
hole-burning to reveal the presence of three conformations for Ac-β ACP C -γ ACHC -NHBz, and a single conformation
for Ac-γ ACHC -β ACP C -NHBz. Resonant ion-dip infrared (RIDIR) spectra were obtained in the NH stretch region from
3300 to 3500 cm−1 and in both the amide I and II regions from 1400 to 1800 cm−1 . These spectra were compared to
computational predictions given by DFT calculations using the M05-2X functional with a 6-31G+(d) basis set revealing
two slightly varied iterations of a bifurcated C-8/13 double ring structure for Ac-β ACP C -γ ACHC -NHBz and one bifurcated
C-9/13 double ring structure for Ac-γ ACHC -β ACP C -NHBz. The appearance of C-13 rings was also seen in solution phase
studies.a This work is a complement to studies performed on pure γ-peptides and α/γ-peptides.
a L.
Guo, A. M. Almeida, W. Zhang, A. G. Reidenbach, S. H. Choi, I.. A. Guzei, and S. H. Gellman J. Am. Chem. Soc. 2010, 132, 7868-7869
250
WI13
15 min 5:04
ACTION IRMPD SPECTROSCOPY OF B2 FRAGMENT IONS FROM QAXIG AND NAXIG PENTAPEPTIDES
L. MORRISON, Department of Chemistry, The Ohio State University, Columbus, OH 43210; J. CHAMOTROOKE, Department of Mass Spectrometry and Proteomics Research, Pasteur Institute, Paris, France;
V. WYSOCKI, Department of Chemistry, The Ohio State University, Columbus, OH 43210.
The N-terminal fragments of peptides in MS/MS studies, or “b” ions, have been the subject of controversy for many years.
The result of amide bond cleavage, these ions can be generated by two main pathways, forming either a head-to-tail cyclic
peptide or a 5-membered oxazolone ring structure. The b2 ion is particularly interesting because the head-to-tail isomer,
or diketopiperazine, is typically more stable than the oxazolone but requires a high energy trans-cis isomerization of the
peptide bond in order to form. Although amino acid identity in the first two positions is known to influence diketopiperazine
vs. oxazolone formation, the factors that influence diketopiperazine formations are still incompletely understood.
Action IRMPD (infrared multi-photon dissociation) spectroscopy was used to interrogate the gas-phase structures of the
b2 ions from QAXIG and NAXIG (X = L, D, or E) peptides. Irradiation of b2 ions in the 1000 to 2000 cm−1 range
interrogates the amide, amine, and carbonyl vibrational modes characteristic of diketopiperazine and oxazolone b2 ions.
Examination of the b2 structures of QAXIG and NAXIG peptides by this strategy has yielded novel information regarding
the formation pathway of the diketopiperazine structure in the gas phase. Peptides without a basic residue in one of the
first two positions are shown to generate diketopiperazine b2 ions, which suggests that a bridging side chain is critical for
b2 ion formation by this pathway. Moreover, the third residue is shown for the first time to play a role in discriminating
between the oxazolone and diketopiperazine product ions.
WI14
15 min 5:21
MODIFCATION OF THE PROLYL RING OF VAL-PRO-ALA AND THE IMPACT OF THIS MODIFICATION ON B2
ION STRUCTURE
MATTHEW C. BERNIER, VICKI H. WYSOCKI, THE OHIO STATE UNIVERSITY, COLUMBUS, OH;
ASHLEY GUCINSKI, U. S. FDA, SAINT LOUIS, MO; JULIA CHAMOT-ROOKE, INSTITUT PASTEUR,
PARIS, FRANCE.
Here we present b2 ion studies on one tripeptide (VPA) and show how the addition of a fluorine or a hydroxyl group on the
3rd position of the proline ring can affect the b2 ion formation. Action IRMPD results of ValHyp (Hyp=hydroxyproline),
ValFlp (Flp=trans-fluoroproline), and Valflp (flp=cis-fluoroproline) all show the presence of a strong oxazolone band in
the CO region at 1900 cm-1. The presence of peaks in the diketopiperazine region between 1700 and 1800 cm-1 varies
depending on which substituent is placed on the prolyl ring. Recently published data from our group showed a pair of
medium sized diketopiperazine bands at 1760 and 1701 cm-1 for ValPro and we observed similarly intense bands for
Valflp at 1752 and 1689 cm-1. ValHyp and ValFlp fail to show any significant diketopiperazine bands, but if zoomed in
x10 a small band can be observed at 1756 cm-1 for ValHyp. From this data it is apparent that substitution of the second
position prolyl ring can alter the formation of the b2 diketopiperazine ion.
251
WJ. RADICALS AND IONS
Chair: MITCHIO OKUMURA, California Institute of Technology, Pasadena, CA
WJ01
THE INFRARED AND NEAR-INFRARED SPECTRUM OF HNO TRAPPED IN SOLID NEON
15 min 1:30
Although the positions of the vibrational fundamentals of HNO—an important reaction intermediate in the chemistry of
combustion and of the terrestrial atmosphere—have been definitively established for more than thirty years, very little is
known about the behavior of its vibrational overtones and combination bands. Moreover, its NH-stretching fundamental,
which is anomalously low in frequency, blue-shifts when HNO is trapped in solid argon. Measurement of the infrared
and near-infrared spectra of HNO trapped in solid neon explore this latter phenomenon and provide the first experimental
measurement of the positions of several of its overtones and combination bands.
WJ02
A NEW TYPE OF VIBRONIC INTERACTION IN THE NITRATE FREE RADICAL NO3
15 min 1:47
E. HIROTA, The Graduate University for Advanced Studies, Hayama, Kanagawa 240-0193, Japan.
A new type of vibronic interaction is proposed to replace the traditional explanation for the observation of the nu4 progression in the photoelectron spectra of the nitrate anion. The proposal is based upon the high-resolution infrared spectroscopic
results that the first-order Coriolis coupling constant is found to include the contributions not only from the degenerate vibrational mode, but also from the angular momentum of the unpaired electron. In sharp contrast with the traditional model,
which requires a large off-diagonal vibronic interaction matrix element between the ground and excited electronic states,
the new model points out that the fundamental state of a degenerate vibrational mode in the ground electronic state manifold intrinsically bears the character of the excited degenerate electronic state, thereby eliminating structural distortions of
the NO3 neutral molecule caused by a huge Herzberg-Teller effect, as predicted by the traditional treatment.
252
WJ03
15 min 2:04
DISPERSED FLUORESCENCE SPECTROSCOPY OF THE B̃ E – X̃
and 15 NO3
2
′
2
A′2
TRANSITION OF JET COOLED 14 NO3
We have generated NO3 in supersonic free jet expansions and observed laser induced fluorescence ( LIF ) of the B̃ 2 E ′ – X̃
2 ′
A2 transition. We have measured LIF excitation spectra and dispersed fluorescence ( DF ) spectra from the single vibronic
levels ( SVL’s ) of the B̃ 2 E ′ state of 14 NO3 and 15 NO3 . The vibrational structure of the X̃ 2 A′2 state has been analyzed by
comparing the vibrational structures of the DF spectra of the two isotopomers. The 1,053 cm−1 band of 14 NO3 is observed
as two bands at 1,039 and 1,053 cm−1 with an intensity ratio of 4 : 5, respectively, for 15 NO3 , which are observed in the
DF spectra with our standard resolution ( ∼ 7 cm−1 in FWHM ). Higher resolution measurements ( ∼ 2 cm−1 in FWHM )
of the DF spectra show that the 1,053 cm−1 band of 14 NO3 is also observed as two bands at 1,051 and 1,056 cm−1 with
an intensity ratio of 5 : 3, respectively. The 1,051 cm−1 band is attributed to be the ν1 ( a1 ’ ) fundamental, because of its
little isotope shift. There are two possibilities for another band, the band at 1,056 and 1,038 cm−1 for 14 NO3 and 15 NO3 ,
respectively; (1) the ν3 ( e′ ) fundamental banda , and (2) the ν2 + ν4 ( a′′2 and e′ , respectively ) combination band. If
this is the case (1), the ν3 band should be observed in IR spectrum, but it has yet to be observed. If (2), the intensity
must be stolen from the B̃ 2 E ′ – Ã 2 E ′′ transition through the ν2 mode, the considerable transition moment of which has
been predictedb. A simple consideration for the vibronic couplingc between the Ã 2 E ′′ and X̃ 2 A′2 states through the ν2
mode can understand about 20 % of the combination band intensity to that of the ν1 fundamental. The higher resolution
measurements of the DF spectra also show that the 1,499 cm−1 band of 14 NO3 is much stronger than the 1,492 cm−1 band
in the electronic spectrum, while the latter is the strongest band in the IR absorption spectrumd .
a J.
F. Stanton, J. Chem. Phys. 126, 134309 (2007).
F. Stanton and M. Okumura, Phys. Chem. Chem. Phys. 11, 4742 (2009).
c E. Hirota, K. Kawaguchi, T. Ishiwata, and I. Tanaka, J. Chem. Phys. 95, 771 (1991).
d T. Ishiwata, I. Tanaka, K. Kawaguchi, and E. Hirota, J. Chem. Phys. 82, 2196 (1985).
b J.
WJ04
15 min 2:21
ROTATIONALLY-RESOLVED HIGH-RESOLUTION LASER SPECTROSCOPY AND MAGNETIC EFFECT OF THE
B ← X TRANSITION OF NO3 RADICAL
K. TADA, W. KASHIHARA, S. KASAHARA, Graduate School of Science, Kobe University, Kobe 657-8501,
Japan; M. BABA, Graduate School of Science, Kyoto University, Kyoto 606-8502, Japan; T. ISHIWATA,
Graduate School of Information Sciences, Hiroshima City University, Hiroshima 731-3194, Japan; and E. HIROTA, The Graduate University for Advanced Studies, Kanagawa 240-0193, Japan.
Nitrate radical (NO3 ) acts the important roles in various chemical reactions as an oxidant in the night atmosphere. From the
spectroscopic viewpoint, NO3 is one of the great models for understanding the intramolecular interactions in polyatomic
radical species. In this study, rotationally-resolved high-resolution fluorescence excitation spectra of the 662 nm band in
jet-cooled NO3 have been recorded. This 662 nm band has been reported as the 0 - 0 band of the B 2 E ′ ← X 2 A′2
transition. The observed region was 15070 - 15145 cm−1 . Typical linewidth of the observed rotational lines was about 20
MHz. The absolute wavenumbers of the observed rotational lines were calibrated in the accuracy of 0.0001 cm−1 . There
are more than 3000 rotational lines in the observed region. The rotational assignment was difficult because the rotational
lines seemed to have less regularity. To assign the observed rotational lines clearly, magnetic effect up to 360 G of the
intense rotational lines was also observed. From the analysis of the Zeeman splitting, a part of the rotational lines was
successfully assigned. Additionally, the magnetic g-factors of the ground state and the excited states were determined.
253
WJ05
15 min 2:38
e2
VIBRONIC ANALYSIS OF THE A E STATE OF NO3 RADICAL
′′
TERRANCE J. CODD, MOURAD ROUDJANE, MING-WEI CHENa , and TERRY A. MILLER, Laser Spectroscopy Facility, The Ohio State University, Columbus, Ohio 43210.
The nitrate radical is a key reactant in atmospheric chemistry leading to the formation of acid rain and is the primary
e2 E ′′ state of NO3 is doubly degenerate and is therefore subject to Jahn-Teller (JT) coupling
oxidant in the night sky. The A
through the degenerate in-plane stretch and bend modes (ν3 and ν4 respectively). We have taken a moderate resolution
e2 E ′′ -X
e 2 A′ transition of the NO3 radical under jet-cooled conditions. We resolve ∼ 20 vibronic
CRDS spectrum of the A
2
transitions and are able to assign many using an independent anharmonic oscillator model as was presented previously.b
In order to gain a deeper understanding of the nature of the JT effect in this electronic state we have performed a vibronic
analysis including linear and quadratic JT coupling terms for ν3 and ν4 and possible bilinear coupling between the totally
symmetric stretch, ν1 , and ν4 . We conclude that the JT coupling in ν4 is quite weak. Satisfactory spectral fits can be
obtained assuming weak JT coupling for ν3 also, though there is some evidence of strong JT coupling for ν3 and the
strengths and weaknesses of each case are discussed.
a Present
b Codd,
address: University of Illinois at Urbana-Champaign, Urbana, IL 61801
T. et al. 67th Int. Symp. Molec. Spec. (2012)
WJ06
HIGH RESOLUTION CAVITY RING DOWN SPECTROSCOPY OF THE
OF NO3 RADICAL
15 min 2:55
310
and
310
410
BANDS OF THE Ã2 E′′ STATE
MOURAD ROUDJANE, TERRANCE J. CODD and TERRY A. MILLER, Laser Spectroscopy Facility, The
Ohio State University, Columbus, Ohio 43210.
The NO3 radical is expected to exhibit a Jahn-Teller (JT) effect in its degenerate Ã2 E′′ electronic state.a In the Ã state
there are two JT active modes, ν3 and ν4 (e′ stretch and in-plane bend respectively). Theoretical work has predicted that
the JT effect in the Ã state should be quite strong and approach the static case where the molecule is permanently distorted
to a lower symmetry geometry. A more comprehensive understanding of its structure can be achieved using high resolution
rotationally resolved absorption spectroscopy of its different vibronic bands. The high resolution absorption spectra of
310 and 310 410 vibronic bands of the Ã 2 E′′ excited state of NO3 have been successfully recorded for the first time using
our jet cooled cavity ring down apparatus. These parallel bands are vibronically allowed transitions and shows the same
contour. An oblate symmetric top model Hamiltonian including both centrifugal distortion and spin rotation terms is used
to analyze the spectrum. The rotational analysis of this band, supported by combination differences, demonstrate the
existence of doubled lines as were observed for 4n0 (n=1,3) bands.b
a E.
Hirota, T. Ishiwata, K. Kawaguchi, M. Fujitake, N. Ohashi, and I. Tanaka, J. Chem. Phys., 107, 2829, 1997.
M. et al. 67th OSU International Symposium on Molecular Spectroscopy, The Ohio State University, Columbus, Ohio, 2011, talk TI-03.
b Roudjane,
254
WJ07
15 min 3:12
THE RENNER-TELLER AND JAHN-TELLER EFFECTS IN PROTOTYPICAL MOLECULAR CATIONS SUBJECT
TO A VERY LARGE SPIN-ORBIT COUPLING
BÉRENGER GANS, MONIKA GRÜTTER and FRÉDÉRIC MERKT, Laboratorium für Physikalische
Chemie, ETH Zürich, CH-8093 Zürich, Switzerland.
PFI-ZEKE photoelectron spectra of the X+ 2 Π ← X 1 Σ+ transition of HC2 I and of the X̃+ 2 E3/2 ← X̃ 1 A1 transition of
CH3 I have been recorded at a resolution sufficiently high to observe, at least partially, their rotational structure. The spinrovibronic energy-level structures of HC2 I+ and CH3 I+ could be determined at low energies and enabled us to study the
Renner-Teller and Jahn-Teller effects in molecular cations subject to a very large spin-orbit coupling with unprecedented
details.
In the case of HC2 I, the nominally forbidden 510 band has been observed in addition to the origin band and allowed us
to determine a splitting of 2 cm−1 between the two Renner-Teller components of the 51 vibrational level of the cation.
In the case of CH3 I, the rotational structure of the origin and of the 210 and 310 bands are dominated by satellite bands of
spin-rovibronic origina . The 510 and 610 bands reveal an additional splitting corresponding to the separation between the two
Jahn-Teller components of j = 1/2 and j = 3/2 symmetry of the 51 and 61 levels of the cationb .
a M.
Grütter, J.M. Michaud and F. Merkt, J. Chem. Phys. 134, 054308 (2011).
Barckholtz and T.A. Miller, Int. Rev. Phys. Chem. 17 (4), 435 (1998).
b T.A.
WJ08
OBSERVATION OF THE a1 CH STRETCHING MODES OF PHENYL RADICAL
15 min 3:29
CHIH-HSUAN CHANG, GRANT T. BUCKINGHAM, DAVID J. NESBITT, JILA, National Institute of Standards and Technology University of Colorado, and Department of Chemistry and Biochemistry University of
Colorado at Boulder, Colorado 80309.
High resolution spectroscopy for infrared rovibrational transitions in the CH stretching manifold of phenyl radical (C6 H5 )
has been investigated in the slit-jet supersonic expansion at sub-Doppler resolution (60 MHz). Two new fundamental
modes are observed and analyzed in this present study, corresponding to b-type structure originating from excitation of
the fundamentals v 1 and v 2 mode. The band origins are determined to be 3073.96850(8) cm−1 and 3062.26480(7) cm−1 ,
respectively, which agree well with theoretical anharmonic scaling prediction within 5 cm−1 based on the B3LYP/6311g++(3df,3dp) basis set, but shifted by 11 cm−1 from the corresponding experimental Ar-matrix’s results of Ellison and
coworkersa. Intensities for the three bands are also analyzed, with the relative intensities between these three agreeing
well with theoretical calculation. The physical interpretation of the inertia defect and perturbations of the band positions
to explain the experimental observation and the frequencies shift.
a Anders. V. Friderichsen, Juliusz G. Radziszewski, Mark R. Nimols, Paul R. Winter, David C. Dayton, Donald E. David, and G. Barney Ellison, J.
Am. Chem. Soc. 123, 1977 (2001)
255
WJ09
15 min 3:46
HIGH RESOLUTION ROVIBRATIONAL SPECTROSCOPY OF JET-COOLED PHENYL RADICAL: THE ν19 OUTOF-PHASE SYMMETRIC C-H STRETCH
GRANT T. BUCKINGHAM, CHIH-HSUAN CHANG, and DAVID J. NESBITT, JILA, National Institute of
Standards and Technology and University of Colorado, Department of Chemistry and Biochemistry, Boulder,
CO 80309.
Phenyl radical has been studied via sub-Doppler infrared spectroscopy in a slit supersonic discharge expansion source, with
assignments for the highest frequency b2 out-of-phase C-H symmetric stretch vibration (ν19 ) unambiguously confirmed by
≤ 6 MHz (0.0002 cm−1 ) agreement with microwave ground state combination differences of McMahon et al. [Astrophys.
J. 590, L61-64 (2003)]. Least squares analysis of > 100 resolved rovibrational peaks in the sub-Doppler spectrum to a
Watson Hamiltonian yields precision exited-state rotational constants and a vibrational band origin (ν0 = 3071.8915(4)
cm−1 ) consistent with a surprisingly small red-shift (0.9 cm−1 ) with respect to Ar matrix isolation studies of Ellison and
coworkers [J. Am. Chem. Soc. 123, 1977 (2001)]. Nuclear spin weights and inertial defects confirm the vibrationally
averaged planarity and 2 A1 rovibronic symmetry of phenyl radical, with analysis of the rotational constants consistent
with a modest C2v distortion of the carbon backbone frame due to partial sp rehybridization of the σ C radical-center.
Most importantly, despite the number of atoms (N = 11) and vibrational modes (3N−6 = 27), phenyl radical exhibits a
remarkably clean jet cooled high resolution IR spectrum that shows no evidence of intramolecular vibrational relaxation
(IVR) phenomena such as local or non-local perturbations due to strongly coupled nearby dark states. This provides strong
support for the feasibility of high resolution infrared spectroscopy in other cyclic aromatic hydrocarbon radical systems.
Intermission
WJ10
MOLECULAR CONSTANTS OF C2 IN THE c
15 min 4:20
3
Σ+
u
STATE
MASAKAZU NAKAJIMA and YASUKI ENDO, Department of Basic Science, The University of Tokyo,
Tokyo 153-8902, Japan.
The d3 Πg − c3 Σ+
u band system of C2 was observed in a discharge flow cell by laser induced fluorescence spectroscopy.
Although the observation of the band system has been reported for the jet-cooled C2 molecule, a transitions involving
higher rotational levels were observed in the present study. Improved molecular constants for several vibrational levels of
′′
the c3 Σ+
u state will be presented. Furthermore, the bands with v = 5, 6, 7 were newly observed in a discharged supersonic
jet, of which molecular constants were determined for the first time.
a J.
A. Joester et al., J. Chem. Phys. 127, 214303 (2007).
256
WJ11
15 min 4:37
RE-ANALYSIS OF THE SPIN-ORBIT PERTURBATION FOR THE PHILLIPS SYSTEM AND THE BALLIKRAMSAY SYSTEM OF THE SPECTRA OF C2
WANG CHEN, JIAN TANG and KENTAROU KAWAGUCHI, Graduate School of Natural Science and Technology Okayama University, 3-1-1 Tsushima-Naka, Okayama 700-8530, Japan.
The Phillips system and the Ballik-Ramsay system of the spectra of C2 have been studied extensively before, and the
3
energy difference between the ground X 1 Σ+
g state and the first triplet a Πu state has been determined by analyzing the
1 +
3 −
spin-orbit interaction between the X Σg and b Σg states. However, the analysis was carried out previously for the
individual vibronic bands, and the perturbation parameters < v|HSO |v ′ > of the spin-orbit interaction determined for
a,b
the different vibronic states lead to the very different values of AbX
In the present study, we re-analyzed the previous
so .
a,c,d
spectral data
by using the overlap integrals (Franck-Condon factors) and r-centroids between the vibronic states of
3 −
X 1 Σ+
g and b Σg calculated from the RKR potential and by fitting all the vibronic states simultaneously. A new set of
−1
molecular parameters was obtained, including the single-valued spin-orbit interaction constant AbX
and
so = 3.067(9) cm
−1
1 +
3
the energy difference ∆E = 719.84(6) cm between the X Σg and a Πu states, the latter of which is about 1.5 cm−1
larger than the previously determined value.a This new result may guide for searching the forbidden transitions between
the singlet and triplet states of C2 .
a C.
Amiot, J. Chauville and J. -P. Maillard, J. Mol. Spectrosc. 75, 19 (1979).
P. Davis et al., J. Opt. Sol. Am. B. 5, 1838 (1988).
c M. Douay, R. Nietmann and P. -F. Bernath, J. Mol. Spectrosc. 131, 250 (1988).
d M-C. Chan et al., Chem. Phys. Lett. 390, 340 (2004).
b S.
WJ12
15 min 4:54
THE ETHYL RADICAL IN SUPERFLUID HELIUM NANODROPLETS: ROVIBRATIONAL SPECTROSCOPY AND
AB INITIO CALCLUATIONS
PAUL L. RASTON, CHRISTOPHER P. MORADI, Department of Chemistry, University of Georgia, Athens,
Georgia 30602-2556; JAY AGARWAL, JUSTIN. M. TURNEY, HENRY F. SCHAEFER III, Center for
Computational Chemistry, University of Georgia, Athens, Georgia 30602-2556; GARY E. DOUBERLY,
Department of Chemistry, University of Georgia, Athens, Georgia 30602-2556.
The ethyl radical has been isolated and spectroscopically characterized in 4 He nanodroplets. The five fundamental CH
stretch bands are observed near 3 µm and have band origins shifted < 1 cm−1 from those reported for the gas phase
species.a,b The symmetric CH2 stretching band (ν1 ) is rotationally resolved, revealing nuclear spin statistical weights
predicted by G12 permutation-inversion group theory. A permanent electric dipole moment of 0.28 (2) D is obtained via
the Stark spectrum of the ν1 band. The four other CH stretch fundamental bands are broadened in helium droplets and
lack rotational fine structure. The approximately 1-2 cm−1 line widths for these bands are attributed to the homogeneous
broadening associated with solvent-mediated rovibrational relaxation dynamics. In addition to these five fundamentals,
three A′1 overtone/combination bands are observed and have resolved rotational substructure. These are assigned to the
2ν12 , ν4 +ν6 , and 2ν6 bands through comparisons to anharmonic frequency computations at the CCSD(T)/cc-pVTZ level
of theory.
a S.
b T.
Davis, D. Uy, D. J. Nesbitt. J. Chem. Phys. 112, 1823-1834 (2000).
Haber, A. C. Blair, D. J. Nesbitt, M. D. Schuder. J. Chem. Phys. 124, 054316 (2006).
257
WJ13
15 min 5:11
INRARED SPECTROSCOPY AND TUNNELING DYNAMICS OF THE VINYL RADICAL IN He NANODROPLETS
4
PAUL L. RASTON, TAO LIANG, EMMANUEL I. OBI, and GARY E. DOUBERLY, Department of Chemistry, University of Georgia, Athens, Georgia 30602, USA.
The vinyl radical has been trapped in 4 He nanodroplets and probed with infrared laser spectroscopy in the CH stretch region
between 2850 and 3200 cm−1 . The assigned band origins for the CH2 symmetric (ν 3 ), CH2 antisymmetric (ν 2 ), and lone
α-CH stretch (ν 1 ) vibrations are in good agreement with previously reported full-dimensional vibrational configuration
interaction calculations.a For all three bands, a-type and b-type transitions are observed from the lowest symmetry allowed
roconvibrational state of each nuclear spin isomer, which allows for a determination of the tunneling splittings in both the
ground and excited vibrational levels. Comparisons to gas phase millimeter-wave rotation-tunnelingb and high-resolution
jet-cooled infrared spectrac reveal that the effect of the 4 He solvent is to reduce the ground and ν 3 excited state tunneling
splittings by ≈20%. This solvent-induced modification of the tunneling dynamics can be reasonably accounted for by
assuming either an ≈2.5% increase in the effective barrier height along the tunneling coordinate or an ≈5% increase in the
effective reduced mass of the tunneling particles.
a A.
R. Sharma, B. J. Braams, S. Carter, B. C. Shepler, and J. M. Bowman, J. Chem. Phys. 130, 174301 2009
Tanaka, M. Toshimitsu, K. Harada, and T. Tanaka, J. Chem. Phys. 120, 3604 2004
c F. Dong, M. Roberts, and D. J. Nesbitt, J. Chem. Phys. 128, 044305 (2008)
b K.
WJ14
15 min 5:28
STRUCTURE AND DYNAMICS OF THE CYCLOPROPENE RADICAL CATION STUDIED BY HIGHRESOLUTION PHOTOELECTRON SPECTROSCOPY
KONSTANTINA VASILATOU, JULIE M. MICHAUD, DENITSA BAYKUSHEVA, GUIDO GRASSI and
FREDERIC MERKT, Laboratorium für Physikalische Chemie, ETH Zürich, CH-8093 Zürich, Switzerland.
High-resolution photoelectron spectra of cyclopropene (c-C3 H4 ) and several of its deuterated isotopomers have been
e + 2 B2 ← X
e 1 A1 ionizing
recorded. From the analysis of the almost fully resolved rotational structure of the origin of the X
transition of c-C3 H4 , c-C3 H3 D, c-C3 H2 D2 , c-C3 HD3 and c-C3 D4 and the observation of several low-lying vibrational
levels of the corresponding cations, we conclude that the cyclopropene cation has an equilibrium structure deviating from
C2v symmetry. We believe that the cation is subject to a large-amplitude tunnelling motion along a mode of a2 symmetry
involving a twist of the CH2 group and an asymmetric out-of-plane bending of the CH units. The reasons for this belief
and also currently unresolved aspects of our analysis will be discussed.
WJ15
15 min 5:45
STRUCTURE DETERMINATION OF NON-LINEAR HYDROCARBON CHAINS BY DEUTERIUM LABELING
P.O. Box 9513, NL-2300 RA Leiden; M. A. HADDAD, W. UBACHS, LaserLaB, VU University Amsterdam,
De Boelelaan 1081, NL-1081 HV, Amsterdam, The Netherlands.
Isotopic labeling is an analytical tool that has been widely used in chemistry and biochemistry. In this contribution, we
illustrate the potential of isotopic labeling in the structure determination of gaseous carbon-chain radicals. More spefically, systematic deuterium labeling experiments are presented for three non-linear hydrocarbon chains (C9 H3 with C2v
symmetry, and two C11 H3 isomers with C2v and Cs symmetries, respectively), where the H/D atoms in these molecules
are chosen as isotopic tracers.a In the experiment, electronic absorption spectra are recorded for these target hydrocarbon chains and their (partially) deuterated equivalents in special hydrocarbon plasma expansions constituting C/H, C/D,
and C/H/D, respectively. The number of observed bands, the quantitative determination of isotopic shifts, and supporting
DFT-calculations make it possible to unambiguously identify the geometric structures of HC4 CHC4 H, HC4 C(C2 H)C4 H,
and HC4 CHC6 H. This result also confirms that optical spectra of D-substituted species can provide molecular symmetry
information of polyhydrides, as well as chemical bond correlations in the substructures containing D-labeled hydrogen.
Deuterium labeling, therefore, is considered as a useful approach to characterize the molecular structure of gaseous hydrocarbons.
a D. Zhao, H. Linnartz, W. Ubachs J. Chem. Phys. 136(5), 054307 2012; and D. Zhao, M. A. Haddad, H. Linnartz, W. Ubachs J. Chem. Phys. 135(7),
074201 2011.
258
WK. ELECTRONIC
Chair: ANTHONY MERER, Academia Sinica, Taipei, Taiwan
WK01
SPECTROSCOPY OF LiCa AND RbSr MOLECULES ON HELIUM NANODROPLETS
15 min 1:30
We report on the investigation of mixed alkali metal (Ak) - alkaline earth metal (Ake) molecules on the surface of helium
nanodroplets (HeN ). These molecules have recently attracted considerable attention as candidates for the formation of
ultracold molecules with a magnetic and an electronic dipole momenta . In our experiments, LiCa and RbSr molecules are
formed in a sequential pick-up process in their X2 Σ+ ground state and cool down rapidly to the droplet temperature of
0.38 Kb . Excitation spectra of LiCa and RbSr were recorded by using resonance enhanced multi-photon ionization timeof-flight (REMPI-TOF) spectroscopy and laser induced fluorescence (LIF) spectroscopy. On the helium droplet, vibronic
transitions in Ak-Ake molecules are broadened and show a characteristic asymmetric peak form, which is caused by
the interaction between the molecule and the superfluid HeN environment. For the lower electronic transitions in LiCa
and RbSr progressions of vibrational bands excited from the X2 Σ+ (ν ′′ = 0) state are observed. The LiCa spectra can
be compared to molecular beam experimentsc, which enables the assignment of three band systems near 15260 cm−1 ,
19300 cm−1 and 22120 cm−1 as 2 Σ+ , 2 ΠΩ and 2 Π band, respectively. In the RbSr excitation spectrum we observe a
vibrationally resolved band system near 14020 cm−1 .
Upon electronic excitation, a fraction of the molecules desorb from the droplet surface and dispersed fluorescence spectra
allow to study the X2 Σ+ ground state and excited states of free Ak-Ake molecules.
a H.
Hara, Y. Takasu, Y. Yamaoka, J.M. Doyle, Y. Takahashi, Phys. Rev. Lett. 106, 205304 (2011)
and W. E. Ernst, Helium Droplets as Nanocryostats for Molecular Spectroscopy - from the Vacuum Ultraviolet to the Microwave Regime,
c L. M. Russon, G. K. Rothschopf, M. D. Morse, A. I. Boldyrev, J. Simons, J. Chem. Phys. 109, 6655-6665 (1998)
b C. Callegari
259
WK02
15 min 1:47
SPECTROSCOPY OF Li ATOMS AND Li DIMERS IN THE TRIPLET MANIFOLD ON THE SURFACE OF HELIUM
NANODROPLETS
Helium nanodroplets (HeN ) have attracted strong interest as superfluid nanocryostats and can serve as a tool for the efficient
preparation of tailored molecules and clustersa . Alkali-metal atoms and molecules are bound only weakly to the HeN
surface. The fragility of these systems leads preferably to the formation of high-spin molecules on HeN bc . We use this
property of helium nanodroplets for the preparation of Li dimers in their triplet ground state (13 Σ+
u ). We present an
′′
excitation spectrum of the 23 Πg (ν ′ = 0 − 10) ← 13 Σ+
(ν
=
0)
transition.
The
interaction
between
the molecule and
u
the droplet manifests in a broadening of the transitions with a characteristic asymmetric form. The broadening extents
to the blue side of each vibronic level, which is caused by the simultaneous excitation of the molecule and vibrations
of the droplet (phonons). The two isotopes of Li form 6 Li2 , 7 Li2 as well as the isotope mixed 6 Li7 Li molecule on the
droplet surface. By using resonance enhanced multi-photon ionization time-of-flight (REMPI-TOF) spectroscopy isotope
dependent effects could be studied.
In addition to excitation spectra of Li molecules, we report on the 3p ← 2s and 3d ← 2s two-photon transitions in
single isolated Li atoms on HeN . From the 2S(Σ) ground state, two-photon transitions into ∆, Π and Σ molecular substates are possible. Mass dependent excitation spectra are recorded by using REMPI-TOF spectroscopy, which allows an
investigation of the exciplex (Li*-Hem , m = 1-3) formation process in the Li-HeN system. Electronic states are shifted and
broadened with respect to free atom transitions, which is explained within the pseudo-diatomic model.
b J. Higgins, C. Callegari, J. Reho, F. Stienkemeier, W.E. Ernst, M. Gutowski and G. Scoles, J. Phys. Chem. A, 102, 4952-4965 (1998)
c J. Higgins, C. Callegari, J. Reho, F. Stienkemeier, W.E. Ernst, K.K. Lehmann, M. Gutowski and G. Scoles, Science, 273, 629-631, (1996)
WK03
OBSERVATION OF THE 5
10 min 2:04
1
Σ+
u
and 5 Πu STATES OF Rb2 BY POLARISATION LABELLING SPECTROSCOPY a
1
JACEK SZCZEPKOWSKI, WODZIMIERZ JASTRZȨBSKI, Institute of Physics, Polish Academy of Sciences, Al. Lotnikóv 32/46, 02-668 Warsaw, Poland ; PAWEŁ KOWALCZYK, ANNA GROCHOLA, Institute
of Experimental Physics, Department of Physics, University of Warsaw, ul. Hoża 69, 00-681 Warsaw, Poland ;
ABDUL-RAHMAN ALLOUCHE, PATRICK CROZET and AMANDA J. ROSS, Institut Lumière Matière,
Université Lyon 1 & CNRS UMR5306, Université de Lyon, France.
Two-colour polarization labeling experiments have been used to explore the excitation spectrum of the rubidium dimer in
the region 25500 - 27000 cm−1 , aiming to establish the symmetry of excited states observed by Han and Heavenb in earlier
work. The spectra we recorded in fact probe quite different electronic states; we identify them from ab initio calculations
1
as the 5 1 Σ+
u and 5 Πu states, dissociating to Rb 5s + Rb 5d atoms. The home-made pulsed laser used to label levels in
the electronic ground state, with nominal linewidth of 0.3 cm−1 , is not sufficiently selective for this heavy-alkali species.
The spectra are a tangled confusion of short and rather irregular progressions of P,R doublets and/or Q lines. We have had
to use cross-correlation techniques to identify transitions seen in different spectra that share a common ground state level,
to establish assignments. Analysis confirms unusual vibrational patterns in the lowest vibrational levels, from avoided
crossings with ion pair states.
a Supported
b J.
by the PAN-CNRS exchange programme, 2011-12
Han, M. Heaven, J. M ol. Spectrosc. 268 37-41 (2011)
260
WK04
5 min 2:16
DOUBLE RESONANCE EXCITATION OF THE RUBIDIUM DIMER : THE 2 Πg STATE
1
ANASTASIA DROZDOVA, Department of Chemistry, Moscow State University, 119991 Moscow, Russia ;
ABDUL-RAHMAN ALLOUCHE, GHASSAN WANNOUS, PATRICK CROZET and AMANDA J. ROSS,
Institut Lumière Matière, Université Lyon 1 & CNRS UMR5306, Université de Lyon, France.
We have performed a series of optical-optical double resonance experiments with one or two cw Ti:sapphire lasers, to excite
the 2 1 Πg state of Rb2 , recording infrared fluorescence from 2 1 Πg on a Fourier transform spectrometer. Fluorescence from
the lower vibrational levels of 2 1 Πg (Te = 22069.56 cm−1 ) is dominated by transitions to the B 1 Πu state studied by Amiot
and Vergèsa . Vibrational and rotational relaxation from laser-pumped levels v’ < 15 now give a rather complete description
around the potential minimum of the 2 1 Πg state, completing the observations for 6 ≤ v ≤ 50 reported by Han et alb last
3
year. Fluorescence from v’ > 35, occurs also to the 0+ components of the A 1 Σ+
u ∼b Πu complex. Fitting all available
1
1
85
85
87
2 Πg →B Πu data for Rb2 and Rb Rb (several thousand transitions) has also given an improved description of the
bottom of the B 1 Πu state potential well. The 2 1 Πg state correlates at long-range with Rb 5s + Rb 4d 2 D3/2 atomsc , giving
a dissociation energy of 1279.6 cm−1 . Most new data lie below v = 45, 250 cm−1 below this dissociation threshold.
a Amiot
and Vergès, Chem. P hys. Lett. 294 91-98 (1997)
Han et al, Chem. P hys. Lett. 538 1-4 (2011)
c A.-R.Allouche, M. Aubert-Frécon, J. Chem. P hys 136 37-41 (2012)
b X.
WK05
15 min 2:23
EXCITATION OF ULTRACOLD MOLECULES TO “TRILOBITE-LIKE" LONG-RANGE MOLECULAR RYDBERG
STATES
M. A. BELLOS, R. CAROLLO, J. BANERJEE, E. E. EYLER, P. L. GOULD, W. C. STWALLEY, Department
of Physics, University of Connecticut, Storrs, CT 06269-3046.
A class of long-range Rydberg molecules, sometimes called “trilobite states", occurs when a ground-state atom is embedded in the electronic cloud of a Rydberg atom.a The bond between the Rydberg atom and the ground-state atom originates
from the low-energy scattering of the Rydberg electron from the ground-state atom. We produce trilobite-like states of
ultracold Rb2 at low principal quantum numbers and at internuclear separations less than 40 bohr. We populate these
states through single-photon ultraviolet transitions starting from molecules in high-lying vibrational levels of the lowest
triplet state. This demonstrates that long-range Rydberg molecules can also be excited through bound-bound transitions,
in addition to previous studies that used free-bound transitions. We also discuss the advantages of a bound-bound pathway.
a C.
H. Greene, A. S. Dickinson, and H. R. Sadeghpour, Phys. Rev. Lett. 85, 2458 (2000).
WK06
HIGH RESOLUTION PHOTOELECTRON SPECTROSCOPY OF
15 min 2:40
Au−
2
and
Au−
4
BY PHOTOELECTRON IMAGING
IKER LEON, ZHENG YANG, and LAI-SHENG WANG, DEPARTMENT OF CHEMISTRY, BROWN UNIVERSITY, PROVIDENCE, RI 02912, USA.
−
We report high resolution photoelectron spectra of Au−
2 and Au4 obtained with a newly-built photoelectron imaging
apparatus. Gold anions are produced by laser vaporization and the desired specie is mass selected and focused into the
collinear velocity-map imaging (VMI) lens assembly. The design of the imaging lens has allowed us to obtain less than
0.9% energy resolution for high kinetic energy electrons ( > 1eV) while maintaining wavenumber resolution for low kinetic
energy electrons. Although gold dimer and tetramer have been studied in the past, we present spectroscopic results under
high resolution. For Au−
2 , we report high resolution spectra with an accurate determination of the electron affinity together
with a complete vibrational assignment, for both the anion and neutral ground states, while for Au−
4 , we are able to resolve
a low frequency mode and obtain accurately the adiabatic detachment energy.
261
WK07
15 min 2:57
INTRACAVITY LASER ABSORPTION SPECTROSCOPY OF PLATINUM NITRIDE IN THE NEAR INFRARED
LEAH C. O’BRIEN, KAITLIN A. WOMACK, Department of Chemistry, Southern Illinois University, Edwardsville, IL 62026-1652; JAMES J. O’BRIEN, SEAN WHITTEMORE, Department of Chemistry, University of Missouri, St Louis, MO 63121-4499.
The (2,0) band of the A2 Σ− - X 2 Π1/2 electronic transition of PtN has been recorded using intracavity laser absorption
spectroscopy. Transitions from 194 P tN , 195 P tN , and 196 P tN isotopologues are observed, as well as the nuclear hyperfine
splitting due to 195 P t with I=1/2. The results of the analysis will be presented and compared with ab initio calculations.
WK08
REANALYSIS OF THE NEAR INFRARED ELECTRONIC TRANSITIONS OF NiCl
10 min 3:14
LEAH C. O’BRIEN, TAYLOR DAHMS, Department of Chemistry, Southern Illinois University, Edwardsville, IL 62026-1652; JAMES J. O’BRIEN, Department of Chemistry, University of Missouri, St Louis,
MO 63121-4499.
Three near infrared electronic transitions of NiCl have been reanalyzed. Hougen’s recent (2011) theoretical investigation of
low-lying states of metal halides with a d9 electronic configuration indicated that the signs of the experimental spin-rotation
and lambda-doubling signs for the low-lying Ω=1/2 states of NiCl were not correct. This problem is corrected by assuming
an excited state with 2 Σ− symmetry instead of 2 Σ+ symmetry. Line positions for the [12.3]2 Σ− - X 2 Π3/2 , [12.3]2 Σ− X 2 Π1/2 , and [12.3]2 Σ− - B 2 Σ+ electronic transitions have been refitted, and the new spin-rotation and lambda-doubling
signs agree with the Hougen theory. The results of the analysis will be presented.
WK09
10 min 3:26
INTRACAVITY LASER ABSORPTION SPECTROSCOPY OF ZIRCONIUM FLUORIDE IN THE NEAR INFRARED
LEAH C. O’BRIEN, JACK C. HARMS, Department of Chemistry, Southern Illinois University, Edwardsville,
IL 62026-1652; JAMES J. O’BRIEN , Department of Chemistry and Biochemistry, University of Missouri, St
Louis, MO 63121-4499.
A new band of ZrF has been recorded in the near-infrared with rotational resolution using intracavity laser absorption spectroscopy. A red-degraded bandhead is observed at 12527cm−1 , and 2 R-branches and 2 P-branches have been identified.
The results of the analysis will be presented. The gas phase ZrF molecules were produced using a zirconium-lined hollow
cathode in an argon-based electric discharge with a small amount of SF6 .
Intermission
262
WK10
15 min 4:00
ROTATIONAL AND HYPERFINE STRUCTURE IN THE [17.6]2.5−X2.5 AND [23.3]2.5−X2.5 TRANSITIONS OF
IRIDIUM MONOXIDE
C. LINTON, D. W. TOKARYK, Physics Department and Centre for Laser, Atomic and Molecular Sciences,
University of New Brunswick, Fredericton, NB, Canada E3B 5A3; A. G. ADAM, J. A. DAIGLE, L. M. ESSON, A. D. GRANGER, A. M. SMITH, Chemistry Department and Centre for Laser, Atomic and Molecular
Sciences, University of New Brunswick, Fredericton, NB, Canada E3B 5A3; T. C. STEIMLE, Department of
Chemistry and Biochemistry, Arizona State University, Tempe,AZ 85287, USA..
Laser induced fluorescence spectra of two electronic transitions, [17.6]2.5 - X2.5 and [23.3]2.5 - X2.5, of IrO have been
obtained at high resolution by using a single mode ring dye laser to excite IrO molecules in a laser-ablation molecular beam
source. From spectra taken at the University of New Brunswick at a linewidth of 180 MHz, the 193 IrO - 191 IrO isotope
shifts in the rotational lines established the vibrational assignment of the [23.3]2.5 - X2.5 band as 1 - 0 and confirmed
previous 0 - 0 assignments of the [17.6]2.5 - X2.5 band. The higher J rotational lines of both transitions are observed to
split into closely spaced doublets resulting from quadrupole hyperfine structure caused by the I = 3/2 nuclear spin on both
Ir isotopes. Higher resolution [17.6]2.5 - X2.5 spectra with an approximate linewidth of 30 MHz, were taken at Arizona
State University and showed clearly resolved hyperfine structure in the low J lines. The results of the hyperfine structure
analysis will be discussed as well as (hopefully) Stark and Zeeman effect experiments to determine the permanent electric
and the magnetic dipole moments of IrO.
WK11
ELECTRONIC TRANSITIONS OF YTTRIUM MONOXIDE
15 min 4:17
Y.W. NG, NA WANG, ANDREW B. CLARK and A. S-C. CHEUNG, Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong..
The electronic transition spectrum of yttrium monoxide (YO) in the spectral region between 284nm and 307nm has been
recorded using laser ablation/reaction free-jet expansion and laser induced fluorescence (LIF) spectroscopy. The YO
molecule was produced by reacting laser-ablated yttrium atoms with O2 seeded in argon. Twenty transition bands were
observed in that region and a few bands were selected for further study using optical-optical double resonance (OODR)
spectroscopy. The excited C2 Π state has been reached via the intermediate B2 Σ+ state from the ground X2 Σ+ state.
The excited sub-states observed so far have Ω = 0.5 and 1.5. A least squares fit of the measured rotational lines yielded
molecular constants for the newly observed excited states.
WK12
ELECTRONIC TRANSITIONS OF PALLADIUM AND VANADIUM DIMER
10 min 4:34
YUE QIAN, Y.W. NG, and A. S-C. CHEUNG, Department of Chemistry, The University of Hong Kong,
The laser induced fluorescence (LIF) spectrum of palladium dimer (Pd2 ) in the visible region between 480 and 700 nm
has been studied. Five vibrational bands were recorded and analyzed; they are assigned to a 3 Πg - X3 Σ+
u system. The
−1
vibrational frequency of the ground X3 Σ+
. This is the first experimental
u state has been determined to be 211.4 cm
observation of the LIF spectrum of Pd2 . In addition, the LIF spectrum of vanadium dimer (V2 ) has also been studied;
several new transition band systems were observed in the wavelength between 480 and 530 nm. The analysis of the spectra
recorded for these two molecules will be presented.
263
WK13
ELECTRONIC TRANSITIONS OF RUTHENIUM MONOXIDE
15 min 4:46
NA WANG, Y. W. NG , and A. S-C. CHEUNG, Department of Chemistry, The University of Hong Kong,
The electronic transition spectrum of ruthenium monoxide (RuO) molecule in the spectral region between 545nm to
640nm has been recorded and analyzed using laser ablation/reaction free-jet expansion and laser induced fluorescence
spectroscopy. The RuO molecule was produced by reacting laser- ablated ruthenium atoms with N2 O seeded in argon.
Nine vibrational bands were recorded and they are identified to be belonging to four electronic transition systems, namely
the [18.1]Ω = 4 - X5 ∆4 transition, [16.0]5Φ5 - X5 ∆4 transition, [18.1]Ω = 3 - X5 ∆3 , and [15.8] 5 Φ4 - X5 ∆3 transition.
RuO has been determined to have a X5 ∆4 ground state. A least squares fit of the measured rotational lines yielded molecular constants for the ground and the low-lying electronic states. A molecular orbital energy level diagram has been used
to help with the assignment of the observed electronic states.
WK14
PRECISION SPECTROSCOPY OF TELLURIUM
10 min 5:03
J. COKER, J.E. FURNEAUX, Department of Physics and Astronomy, University of Oklahoma, Norman,
OK 73069.
Tellurium (Te2 ) is widely used as a frequency reference, largely due to the fact that it has an optical transition roughly
every 2-3 GHz throughout a large portion of the visible spectrum. Although a standard atlas encompassing over 5200 cm−1
already exists [1], Doppler broadening present in that work buries a significant portion of the features [2]. More recent
studies of Te2 exist which do not exhibit Doppler broadening, such as Refs. [3-5], and each covers different parts of the
spectrum. This work adds to that knowledge a few hundred transitions in the vicinity of 444 nm, measured with high
precision in order to improve measurement of the spectroscopic constants of Te2 ’s excited states. Using a Fabry Perot
cavity in a shock-absorbing, temperature and pressure regulated chamber, locked to a Zeeman stabilized HeNe laser, we
measure changes in frequency of our diode laser to ∼1 MHz precision. This diode laser is scanned over 1000 GHz for use
in a saturated-absorption spectroscopy cell filled with Te2 vapor. Details of the cavity and its short and long-term stability
are discussed, as well as spectroscopic properties of Te2 .
References:
1. J. Cariou, and P. Luc, Atlas du spectre d’absorption de la molecule de tellure, Laboratoire Aime-Cotton (1980).
2. J. Coker et al., J. Opt. Soc. Am. B 28, 2934 (2011).
3. J. Verges et al., Physica Scripta 25, 338 (1982).
4. Ph. Courteille et al., Appl. Phys. B 59, 187 (1994)
5. T.J. Scholl et al., J. Opt. Soc. Am. B 22, 1128 (2005).
264
WK15
15 min 5:15
IONIZATION MEASUREMENT AND SPECTROSCOPY OF ThS AND ThS
+
J. H. BARTLETT, M. C. HEAVEN, Department of Chemistry, Emory University, Atlanta, GA 30322.
Gas-phase thorium sulfide has been produced via laser ablation of thorium in a jet-cooled expansion of 0.1% H2 S/He carrier
gas. Electronic spectra have been recorded for the first time by laser-induced fluorescence (LIF) over the region 1750023650 cm−1 . Resonance-enhanced multiphoton ionization (REMPI) was used in conjunction with a Wiley-McLaren timeof-flight mass spectrometer to confirm LIF assigments of seven rotationally-resolved bands belonging to ThS. Dispersing
fluorescence from the [22.13]1 Π-X 1 Σg transition revealed a vibrational progression of the ground electronic state of ThS,
for which the vibrational constants were ω e = 520.0(7) cm−1 and ω e χe = 11.0(9) cm−1 . An accurate value for the
ionization potential of ThS as well as term energies of ThS+ up to v+ = 7 in the 2 Σ+ ground state and v+ = 3 in the
2
∆3/2 first excited state have been obtained using two-photon pulsed-field ionization zero kinetic energy photoelectron
spectroscopy (PFI-ZEKE). Vibrational constants for these states have also been detemined. High-level electronic structure
calculations performed for ThS and ThS+ gave term energies and molecular parameters that are in excellent agreement
with the experimental results. The change in bond characteristics upon ionization of ThS is found to be consistent with
that observed for HfO, HfS, and ThO.
WK16
15 min 5:32
A STUDY OF NbCr AND NbCr BY ANION PHOTOELECTRON SPECTROSCOPY
−
MELISSA A. BAUDHUIN, PRAVEENKUMAR BOOPALACHANDRAN, SRIJAY S. RAJAN, and
DOREEN G. LEOPOLD , Department of Chemistry, University of Minnesota, Minneapolis, MN 55455.
We report the 488 nm photoelectron spectrum of the NbCr− anion. For the 2 ∆ ground state of neutral NbCr, the short bond
length (1.894 Å) and high bond energy (D0 3.0263(6) eV) measured by R2PI spectroscopya indicate high order multiple
bonding. We find that the NbCr− anion has a 1 Σ+ ground state, in which the "extra" electron occupies the (4d)δ bonding
orbital, giving a 1σ 2 1π 4 1δ 4 2σ 2 valence electron configuration and a formal bond order of 6. Low-lying excited states of
NbCr (assigned as two 2 Σ+ states) and NbCr− (3 ∆) are also observed. The spectra provide the electron affinity of NbCr,
energies of the 2 Σ+ and the 3 ∆ excited states, vibrational frequencies for the NbCr and NbCr− ground states and for the
2 +
Σ excited states, and (from Franck-Condon analyses) differences among the bond lengths of the observed states. These
results are compared with our previous data for the Group 5/6 congeners NbMo, VCr, and VMo, and with DFT predictions.
We also report results for ongoing experiments on the flow tube reactions of the Group V metals Nb and Ta with butadiene,
and the vibrationally-resolved photoelectron spectra of some of the organometallic reaction product anions.
a S.
M. Sickafoose, J. D. Langenberg, and M. D. Morse, J. Phys. Chem. A. 104, 3521-3527 (2000).
265
RA. MINI-SYMPOSIUM: THEORY AND SPECTROSCOPY
Chair: JENS-UWE GRABOW, Gottfried-Wilhelm-Leibniz-Universitaet, Hannover, Germany
RA01
INVITED TALK
30 min 8:30
MANIFESTATIONS OF VIBRONIC COUPLING EFFECTS IN MOLECULAR SPECTROSCOPY: FROM THE
QUENCHING OF EXCITONIC ENERGY SPLITTINGS TO THE CLEMENTS BANDS OF SO2
HORST KÖPPEL, Theoretical Chemistry, Institute of Physical Chemistry, University of Heidelberg, D-69120
Heidelberg, Germany.
We investigate the excitation of vibrational modes and its impact on the excitonic energy splittings in doubly hydrogenbonded molecular dimers. The experimental analysis, performed in collaboration by S. Leutwyler and coworkers (Univ.
Bern), is based on high-resolution resonant two-photon ionization spectroscopy. The potential energy surfaces underlying
the theoretical investigation are obtained at the RICC2/aug-cc-pVTZ level and are used for the dynamical analysis in the
framework of a well-established vibronic coupling approach.
The vertical electronic Davydov splitting of the S1 and S2 excited states exceeds the observed excitonic splitting by a factor
of 10–40. This discrepancy can be understood by considering the quenching of the excitonic splitting by the excitation
of vibrational modes in the electronic transition. Two different approaches have been employed and found to reconcile
theory and experiment.a,b The analysis of the vibronic structure of the S2 ← S0 excitation spectrum focusses on the
ortho-cyanophenol dimer as a representative example. Most of the observed spectral features can be reproduced by the
calculations, although some deviations remain.
In the second part, new results on the UV absorption spectrum of SO2 will be presented. This is complementary to the
excitonic systems in that higher vibrational energies are involved and a conical intersection is accessible to the nuclear
motion. Using the concept of regularized diabatic states c in combination with high-accuracy MRCI potential energy
surfaces, semi-quantitative agreement with the complex experimental (low-resolution) spectrum has been achieved for the
first time. d
a P.
Ottiger, S. Leutwyler and H. Köppel, J. Chem. Phys. 136, 174308 (2012).
Kopec, P. Ottiger, S. Leutwyler and H. Köppel, J. Chem. Phys. 137, 184312 (2012).
c H. Köppel and B. Schubert, Mol. Phys. 104, 1069 (2006).
d C. Leveque, A. Komainda, R. Taieb and H. Köppel, J. Chem. Phys. 138, 044320 (2013).
b S.
RA02
15 min 9:05
TUNNELING SPLITTINGS IN VIBRONIC STRUCTURE OF CH3 F (X̃ E): STUDIED BY HIGH RESOLUTION
PHOTOELECTRON SPECTRA AND AB IN IT IO THEORETICAL METHOD
+
2
YUXIANG MO, SHUMING GAO, ZUYANG DAI, and HUA LI, Department of Physics and State Key Laboratory of Low-Dimensional Quantum Physics, Tsinghua University, Beijing 100084, China.
We report a combined experimental and theoretical study on the vibronic structure of CH3 F+ . The results show that the
tunneling splittings of vibrational energy levels occur in CH3 F+ due to the Jahn-Teller effect. Experimentally, we have
measured a high resolution ZEKE spectrum of CH3 F up to 3500 cm−1 above the ground state. Theoretically, we performed
an ab initio calculation based on the diabatic model.a The adiabatic potential energy surfaces (APES) of CH3 F+ have
been calculated at the MRCI/CAS/avq(t)z level and expressed by Taylor expansions with normal coordinates as variables.
The energy gradients for the lower and upper APES, the derivative couplings between them and also the energies of the
APES have been used to determine the coefficients in the Taylor expansion.b The spin-vibronic energy levels have been
calculated by accounting all six vibrational modes and their couplings. The experimental ZEKE spectra were assigned
based on the theoretical calculations.
a W. Domcke, D. R. Yarkony, and H. Köpple (Eds.), Conical Intersections: Eletronic Structure, Dynamics and Spectroscopy (World Scientific, Singapore, 2004).
b M. S. Schuurman, D. E. Weinberg, and D. R. Yarkony, J. Chem. Phys. 127, 104309 (2007).
266
RA03
15 min 9:22
ANALYSIS OF THE ROTATIONALLY-RESOLVED SPECTRA OF THE VIBRONICALLY-ACTIVE MOLECULES
DMITRY G. MELNIK and TERRY A. MILLER, Laser Spectroscopy Facility, Department of Chemistry, The
Ohio State University, 120 W. 18th Avenue, Columbus, Ohio 43210.
Rotational structure of the vibronically coupled, and specifically, Jahn-Teller active molecules in isolated vibronic states
has been studied for the decades, and the corresponding Hamiltonian and relationship of its parameters to the molecular
properties are well-established, at least for the e vibronic states. However, in many cases an isolated state approach, both
for the ground and vibronically excited levels, does not produce satisfactory results either because the experimentally
obtained parameters of such model are not physically transparenta, or the model fails to predict the observed spectrumb
to the experimental accuracy. To circumvent these problems, we develop, from the molecular symmetry standpoint, an
effective coupled state rotational Hamiltonian directly accounting for the interactions within the appropriate subset of the
interacting vibronic states. This approach is expected to be useful for the analysis of the rotational level structure of the
closely-spaced vibronic levels such as those occurring in the vibrationally excited manifolds of the open-shell molecules.
The application of this approach to the spectra of the nitrate radical, NO3 , in the Jahn-Teller active Ã2 E ′′ state, will be
discussed.
a D.
b M.
G. Melnik, T. A. Miller and J. Liu, TI15, 67th Molecular Spectroscopy Symposium, Columbus, 2012
Roudjane, T. J. Codd and T. A. Miller, TI03, 67th Molecular Spectroscopy Symposium, Columbus, 2012
RA04
A THEORETICAL PREDICTION OF ELECTRONIC TRANSITIONS IN C3
15 min 9:39
DAVID W. SCHWENKE, GALINA M. CHABAN, NASA Ames Research Center, Moffett Field, CA 94035.
We have carried out first principle calculations of electronic transitions in C3 . Low lying electronic states have linear
or near linear minima, and thus are characterized by D∞v symmetry labels. The ground state has 1 Σ+
g symmetry, and
can be resonably treated by triatomic bound state codes that assume the Born-Oppenheimer approximation is valid . The
lowest excited state has 1 Πu symmetry, and explicit coupling between electronic and nuclear angular momentum must
be considered: the Renner-Teller effect. We treat this coupling exactly so our results are independent of the choice of
coordinates. Furthermore, the 1 Πu state is perturbed by the lowest triplet state, and we include this coupling as well.
RA05
15 min 9:56
e 2A′′ AND A
e 2A′ ELECTONIC STATES OF HSO/HOS
THE RENNER EFFECT IN THE X
ROMAN I. OVSYANNIKOV, Institute of Applied Physics, Russian Academy of Science, Ulyanov Street 46,
Nizhny Novgorod, Russia 603950, and Physical and Theoretical Chemistry, Faculty of Mathematics and Natural Sciences, University of Wuppertal, D-42097 Wuppertal, Germany; PER JENSEN, Physical and Theoretical Chemistry, Faculty of Mathematics and Natural Sciences, University of Wuppertal, D-42097 Wuppertal,
Germany; TSUNEO HIRANO, Department of Chemistry, Faculty of Science, Ochanomizu University, 2-1-1
Otsuka, Bunkyo-ku, Tokyo 112-8610, Japan.
e 2A′′ and A
e 2A′ electronic states of HSO/HOS. Both electronic states have
We report a theoretical investigation of the X
nonlinear equilibrium geometries and they correlate with a 2 Π state at linearity so that they exhibit the Renner effect. In
highly excited bending states, there is tunneling between two minima (with the H nucleus bound to the O or S nucleus,
respectively) separated by a potential energy barrier of 17224.3 cm−1 . The linear geometry H-O-S is accessible to the
molecule; the corresponding barrier is 11877.3 cm−1 . However, the barrier to the H-S-O linear geometry is 34775.2 cm−1
and we take this geometry to be inaccesible to the molecule since at such a large potential energy, our potential energy
surfaces are not well defined and an an accurate calculation of the rovibronic energies is not possible at the present time.
So in practice we consider only a single Renner effect here, namely that at the H-O-S linear geometry. Three-dimensional
e 2A′′ and A
e 2A′ electronic states of HSO have been calculated ab initio by the MRpotential energy surfaces for the X
SDCI+Q/[aug-cc-pCVQZ (S, O), aug-cc-pVQZ (H)] method, and the global potential energy surfaces for the states have
been constructed. These surfaces have been used, in conjunction with the computer program DR [Odaka et al., J. Mol.
Structure 795, 14 (2006); Odaka et al., J. Chem. Phys. 126, 094301 (2007)], for calculating HSO/HOS rovibronic energies
e 2A′′ and A
e 2A′ . The results and analysis of the ab initio calculations, the rovibronic energies
in the electronic states X
obtained, and analyses of the wavefunction for selected states will be presented.
267
Intermission
RA06
15 min
PHOTODISSOCIATION SPECTROSCOPY OF BARE AND HYDRATED PERMANGANATE IONS
10:30
JORGEN HOUMOLLER, KRISTIAN STOCHKEL, STEEN BRONDSTED NIELSEN, Department of
Physics and Astronomy, Aarhus University, Ny Munkegade 120, 8000 Aarhus C, Denmark; SYDNEY H.
KAUFMAN, J. MATHIAS WEBER, JILA, and Department of Chemistry and Biochemistry, University of
Colorado, Boulder, Colorado 80309, USA.
−
We report electronic spectra of mass-selected MnO−
4 and MnO4 · H2 O using electronic photodissociation spectroscopy.
−
−
Upon photoabsorption, bare MnO4 ions decay by formation of MnO−
3 and MnO2 . In contrast, hydrated permanganate
1
predominantly fragments by loss of the water molecule. The 1 T2 band in the visible spectral region shows a well-resolved
vibrational progression consistent with the excitation of a Mn-O stretching mode. Weaker vibrational signatures are also
observed in the much broader UV absorption bands. The presence of a single water molecule does not perturb the spectrum
of MnO−
4 except for a very small blue shift, while full hydration (i.e. in aqueous solution) leads to a blue shift of up to 800
cm−1 . The experimental data can be used as benchmarks for electronic structure theory methods, which usually predict
electronic spectra in vacuo.
RA07
15 min 10:47
MANIFESTATION OF NONADIABATIC EFFECTS IN THE IR SPECTRUM OF PARA-BENZOQUINONE RADICAL
CATION
KRZYSZTOF PIECH, THOMAS BALLY, Department of Chemistry, University of Fribourg, CH-1700 Fribourg, Switzerland; TAKATOSHI ICHINO and JOHN F. STANTON, Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, TX 78712.
X-irradiation of an Ar matrix doped with p-benzoquinone (PBQ) at 10 K leads to formation of the PBQ radical cation
(PBQ•+ ) and radical anion (PBQ•− ). The IR spectrum of PBQ•+ exhibits broad and dense absorption bands in the 2000
cm−1 and higher energy region. Another characteristic of the spectrum is the presence of three intense peaks in the
lower energy region. Equation-of-motion coupled-cluster calculations have been performed to analyze the spectrum with
the quasi-diabatic model Hamiltonian technique. A spectral simulation based on the model Hamiltonian reproduces the
observed IR spectrum very well, revealing that the electronic transition to the low-lying excited state, Ã 2 B2u ← X̃ 2 B3g ,
is severely affected by nonadiabatic interaction of the two states, to which the aforementioned features are attributed. In
particular, three b1u fundamental peaks for X̃ 2 B3g PBQ•+ gain large intensities from the electronic transition through the
vibronic coupling. On the other hand, transition to another b1u fundamental level (anti-symmetric CO stretch) in the X̃ state
has a diminished intensity due to cancellation of the electronic contribution and the usual dipole derivative contribution.
Furthermore, this b1u level is significantly scrambled with nearby vibronic states of b2u symmetry, which accounts for the
weak broad band experimentally observed in the 1560–1600 cm−1 region.
268
RA08
15 min 11:04
NUMERICALLY EXACT DYNAMICS OF FUNCTIONAL QUANTUM SYSTEMS - APPLICATIONS TO GaAs
QUANTUM DOT QUBITS AND 2-DIMENSIONAL SPECTRA OF VERY LARGE PHOTOSYNTHEITC COMPLEXES
NIKESH S. DATTANI, Oxford University, Department of Chemistry, Oxford, OX1 3QZ, UK.
Functional quantum systems is an emerging research field which includes quantum engineering (the design of technologies
that make use of quantum mechanics to outperform their classical counterparts, such as quantum computers, quantum communication devices, quantum thermometers, quantum telescopes, etc.) and the study of natural processes where quantum
mechanics provides some improvement that cannot be realized with classical mechanics (possible examples are photosynthesis, animal navigation, the sense of smell, etc.). Being able to predict how a quantum mechanical system changes (ie,
how its density matrix changes), given its hamiltonian, is paramount in quantum engineering as one needs to know which
hamiltonian will give the desired outcome. Likewise, being able to predict density matrix dynamics in natural systems can
help in understanding the system’s mechanism, in controlling the system’s processes, and can be helpful if designing a
technology which attempts to mimic a natural process. State of the art techniques for calculating density matrix dynamics of functional quantum systems in real-time, and with numerically exact accuracy, have been developed over the last
year. These techniques will be presented, followed by applications for quantum dot based quantum computing, and for
calculating the 2D spectra of large biological systems.
RA09
15 min 11:21
OBSERVATION AND ANALYSIS OF BOUND → FREE TRANSITION OF ScI3 PHOTOEXCITED IN THE ULTRAVIOLET
LOANN D. POMMAREL, J. DARBY HEWITT, THOMAS C. GALVIN, and J. GARY EDEN, Laboratory
for Optical Physics and Enginnering, Department of Electrical and Computer Engineering, University of
Illinois at Urbana-Champaign, 607 East Healey Street, Champaign, IL 61820.
Bound to free transitions of ScI were observed for the first time after photoexcitation of ScI3 in the ultraviolet by 193 nm
radiation from an ArF excimer laser. Broad fluorescence features typical of molecular transitions between different vibrational energy levels of Sc*+I have been measured in the near-infrared between 860 and 940 nm.
Many narrow spectral lines have also been observed, but were attributed to fluorescence of atomic Scandium or Iodine.
Experimental and simulation results will be compared and presented.
RA10
EXCITED STATES OF THE DIATOMIC MOLECULE CrHe
15 min
11:38
JOHANN V. POTOTSCHNIG, MARTIN RATSCHEK, ANDREAS W. HAUSER and WOLFGANG E. ERNST, Institute of Experimental Physics, TU Graz, Petersgasse 16, 8010 Graz, Austria.
Chromium (Cr) atoms embedded in superfluid helium nanodroplets (HeN ) have been investigated by laser induced fluorescence, beam depletion and resonant two-photon ionization spectroscopy in current experiments at our institute. Cr is
found to reside inside the HeN in the a7 S ground state. Two electronically excited states, z7 P and y7 P, are involved in a
photoinduced ejection process which allowed us to study Fano resonances in the photoionisation spectraa . The need for
a better understanding of the experimental observations triggered a theoretical approach towards the computation of electronically excited states via high-level methods of computational chemistry. Two well-established, wave function-based
methods, CASSCF and MRCI, are combined to calculate the potential energy curves for the three states involved. The
character of the two excited states z7 P and y7 P turns out to be significantly different. Theory predicts the ejection of the Cr
atom in the case of an y7 P excitation as was observed experimentallyb. The quasi-inert helium environment is expected to
weaken spin selection rules, allowing a coupling between different spin states especially during the ejection process. We
therefore extend our theoretical analysis to the lowest state in the triplet- and quintet- manifold. Most of these alternative
states show very weak bonding of only a few cm−1 .
a A.
b A.
Kautsch, M. Hasewend, M. Koch and W. E. Ernst, Phys. Rev. A 86, 033428 (2012).
Kautsch, M. Koch and W. E. Ernst, J. Phys. Chem. A, accepted, doi:10.1021/jp312336m
269
RA11
15 min
11:55
POLARIZATION EFFECTS AND IONIC BONDING IN A POLAR DIATOMIC: THE CaF X Σ STATE
+
1
+
STEPHEN L. COY, JOSHUA H. BARABAN, ROBERT W. FIELD, MIT Dept. of Chemistry, Cambridge, MA
02139; BRYAN M. WONG, Materials Chemistry Dept., Sandia National Lab., Livermore, CA 94551.
Core multipoles and polarization effects affect the term values and spectroscopy of Rydberg states, and, conversely, Rydberg state spectroscopy provides a window into the nature of ground electronic state charge distributions, and into polarization due to configuration interaction. As experimental resolution continues to increase through the introduction of
techniques like chirped mm-wave techniques for Rydberg systems, more details about the core electronic structure as a
function of Rydberg state quantum numbers (n,ℓ) and internuclear separation, R, will become available. Existing modeling of the CaF Rydberg spectrum, although extensive, is not ready for the challenge of higher resolution measurements.
Even for the existing data, MQDT calculations (based on a two center effective potential with limited atomic polarization)
show reasonable agreement at equilibrium R, but deviates from the phenomenological QDT fit with R.
We have performed a series of all-electron calculations for CaF+ itself, and for CaF+ with a test negative charge fixed at
distances and angular positions around the core with a range of R, with a goal of improving our understanding of the nature
and magnitude of polarization effects for polar diatomics like CaF. In analyzing these results, we have considered core moments through the octupole, and polarizabilities and hyperpolarizabilities defined in perturbation theory to 4th order that
contribute to the e− -core energy in first and second order. Polarization contributes to ab-initio energies with characteristic
(r, θ) dependence that allows the contributions to be identified by type and as a function of R. Terms describing asymmetric polarization like dipole-dipole and dipole-octopole are found to contribute more strongly than symmetric terms
like quadrupole-quadrupole. The fields present in the e− -core interaction are so high that the F- anion polarizability is
approaching saturation at R = Req = 3.54a0 , while the Ca+2 polarizability is still independent of R.
We will describe the energy expression in the simple effective potential, describe the more complete form including multipolar and polarization terms in Cartesian and spherical coordinates, present two methods for determining polarizabilities,
and compare these ab-initio results with the limited experimental information currently available.
270
RB. RADICALS AND IONS
Chair: HEATHER ABBOTT-LYON, Kennesaw State University, Kennesaw, GA
RB01
15 min 8:30
VIBRATIONAL SPECTROSCOPY OF SYMPATHETICALLY COOLED CaH MOLECULAR IONS
+
NCAMISO B. KHANYILE, JAMES E. GOEDERS and KENNETH R. BROWN, Department of Chemistry,
Georgia Institute of Technology, Atlanta, GA 30332.
The search for time variation in the fundamental constants of nature such as the fine structure constant(α) and the proton/electron mass ratio(µ), is an area of active researcha .Comparing the vibrational overtones of CaH+ with electronic
transitions in atoms has been proposed as a means to detect possible time variation of µ b . Before these precision measurements can be realized, the survey spectroscopy needs to be performed. We describe our experiments using a Coulomb
crystal of sympathetically cooled CaH+ and laser-cooled Ca+ ions to measure the vibrational overtones by resonanceenhanced multiphoton photo-dissociation (REMPD) in a linear Paul trap. The dissociation of CaH+ is detected by observing the change in the crystal composition by monitoring the Ca+ fluorescence. Future single ion experiments for the
precision measurement are also discussed.
a J.
Uzan, Rev. Mod. Phys. 75, 403 (2003).
Kajita and Y. Moriwaki, J. Phys. B: At. Mol. Opt. Phys. 42, 154022(2009).
b M.
RB02
INTRACLUSTER REACTIONS IN Ni-CO2 CLUSTERS
15 min 8:47
JONATHON A. MANER, MATTHEW D. McDOWELL and MICHAEL A. DUNCAN, Department of Chemistry, University of Georgia, Athens, Georgia 30602..
Ni-CO2 cluster cations were produced by laser vaporization of a Ni rod in a pulsed CO2 expansion. Clusters were massselected in a time-of-flight mass spectrometer and studied with infrared laser photodissociation spectroscopy using an
infrared OPO laser system. The infrared spectra of larger clusters provide evidence for an intracluster reaction assisted by
CO2 solvation. These spectra are compared to determine the reaction product.
RB03
15 min 9:04
INFRARED PHOTODISSOCIATION SPECTROSCOPY OF METAL OXIDE CARBONYL CATIONS.
ANTONIO D. BRATHWAITE, MICHAEL A. DUNCAN, Department of Chemistry, University of Georgia,
Athens, GA 30602-2256; ,.
Mass selected metal oxide-carbonyl cations of the form MOm (CO)+
n are studied via infrared laser photodissociation spectroscopy, in the 600-2300cm1 region. Insight into the structure and bonding of these complexes is obtained from the
number of infrared active bands, their relative intensities and their frequency positions. Density functional theory calculations are carried out in support of the experimental data. Insight into the bonding of CO ligands to metal oxides is obtained
and the effect of oxidation on the carbonyl stretching frequency is revealed.
271
RB04
15 min 9:21
ACCURATE POTENTIAL ENERGY CURVES FOR THE GROUND ELECTRONIC STATES OF NeH AND ArH+
+
JOHN A. COXON, Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, Canada B3H 4J3;
Cyprus.
All available microwave and infrared spectroscopic line positions for the ground electronic states of the molecular cations
NeH+ and ArH+ were employed in a direct potential fitting procedure to determine compact analytical potential curves
and radial functions describing breakdown of the Born-Oppenheimer approximation. For NeH+ , 17 adjustable parameters
were required to represent a total of 183 line positions for 4 isotopologues, whereas for ArH+ , 23 adjustable parameters were required to represent 440 line positions for 6 isotopologues. The MLR3 potential energy functional form was
employed, taking full account of the proper 1/r4 limiting long-range dependence of the ion-atom dispersion energy interactions. Accurate vibrational energies, rotational constants and centrifugal distortion constants have been calculated for
both diatomic cations.
RB05
15 min 9:38
EXPANSION DISCHARGE SOURCE FOR ION BEAM LASER SPECTROSCOPY OF COLD MOLECULAR IONS
MICHAEL PORAMBO, JESSICA PEARSON, CRAIG RICCARDO, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801; BENJAMIN J. McCALL, Departments of Chemistry and Astronomy, University of Illinois at Urbana-Champaign, Urbana, IL 61801.
Molecular ions are important in several fields of research, and spectroscopy acts as a key tool in the study of these ions.
However, problems such as low ion abundance, ion-neutral confusion, and spectral congestion due to high internal temperatures can hinder effective spectroscopic studies. To circumvent these problems, we are developing a technique called
Sensitive, Cooled, Resolved, Ion BEam Spectroscopy (SCRIBES). This ion beam spectrometer will feature a continuous
supersonic expansion discharge source to produce cold molecular ions, electrostatic ion optics to focus the ions into an ion
beam and bend the beam away from co-produced neutral molecules, an overlap region for cavity enhanced spectroscopy,
and a time-of-flight mass spectrometer. When completed, SCRIBES will be an effective tool for the study of large, fluxional, and complex molecular ions that are difficult to study with other means. The ion beam spectrometer has been
successfully implemented with a hot ion source.a This talk will focus on the work of integrating a supersonic expansion
discharge sourceb into the instrument. To better understand how the source would work in the whole ion beam instrument,
characterization studies are being performed with spectroscopy of HN+
2 in a section of the system to ascertain the rotational
temperature of the ion expansion. Attempts are also underway to measure the ion current from a beam formed from the
expansion. Once the source in this environment is properly understood, we will reintegrate it to the rest of the ion beam
system, completing SCRIBES.
a A.
b K.
A. Mills, B. M. Siller, M. W. Porambo, M. Perera, H. Kreckel and B. J. McCall J. Chem. Phys., 135, 224201, (2011).
N. Crabtree, C. A. Kauffman and B. J. McCall Rev. Sci. Instrum. 81, 086103, (2010).
Intermission
RB06
15 min
INFRARED PHOTODISSOCATION SPECTROSCOPY OF METAL BENZENE CATION COMPLEXES
10:15
K. N. REISHUS, M. A. DUNCAN, Department of Chemistry, University of Georgia, Athens, GA 30602-2256.
M+ − Bzn complexes are produced in a laser vaporization/supersonic expansion source. These complexes are mass selected in a time-of-flight mass spectrometer, and their infrared spectra (700-4500 cm−1 ) are taken using infrared laser
photodissociation spectroscopy via the argon tagging method. DFT on the M+ − Bzn complexes is carried out to obtain
the structures and vibrational frequencies. The CH stretch and fingerprint regions of the complexes are compared to theory
and the free benzene spectrum. The far infrared spectra of Al+ − Bz and V+ − Bz (700-1800 cm−1 ) are compared to the
previous spectra collected using IR-MPD and significant differences in linewidth and line position are observed.
272
RB07
15 min 10:32
SPECTROSCOPY OF BENZYL-TYPE RADICALS GENERATED BY ELECTRIC DISCHARGE : JET-COOLED
DICHLOROBENZYL RADICALS
YOUNG WOOK YOON and SANG KUK LEE, Department of Chemistry, Pusan National University, Pusan
609-735, Republic of Korea.
The technique of corona excited supersonic expansion coupled with a pinhole-type glass nozzle has been proved a useful
laser-free spectroscopic tool for observation of vibronic emission spectra of large aromatic molecules, especially for molecular radicals which are long believed to play an important role as a reaction intermediate in aromatic chemical reactions.
The vibronic emission spectra recorded with a long-path monochromator exhibit the electronic transition energy in the D1
→ D0 transition and vibrational mode frequencies at the D0 state. In this laboratory, all six isomeric dichlorobenzyl radicalsab have been produced from the corona discharge of corresponding dichlorotoluenes seeded in a large amount of inert
carrier gas He. The vibronic emission spectra show very weak intensity due to the existence of Cl atoms in the precursor
molecules and possible breakdown of benzene ring by free Cl atoms. Nevertheless, we clearly identified the origin band
and a few well-known vibrational modes for each isomer. From an analysis of the spectra observed, we determined the
energy of electronic transition and several vibrational modes in the ground electronic state. Also, the red-shift of the origin
band from the parental benzyl radical clearly shows the substituent effect of Cl atoms on electronic energy, for which we
satisfactorily explain in terms of the shape of the molecular planes and position of the nodal points at a given electronic
state, recently developed in this laboratory for identification of isomeric multi-substituted benzyl-type radicals.
a Y.
b S.
W. Yoon, C. S. Huh, and S. K. Lee, Chem. Phys. Lett. 550, 58 (2012).
K. Lee and S. J. Kim, Chem. Phys. Lett. 412, 88 (2005).
RB08
15 min
10:49
ROVIBRATIONAL SPECTROSCOPY OF THE OH-O3 AND C2 H4 -O3 COMPLEXES IN He NANODROPLETS
4
EMMANUEL I. OBI, and GARY E. DOUBERLY, Department of Chemistry, University of Georgia, Athens,
Georgia 30602, USA.
The weakly bound complexes X-O3 (X=OH, C2 H4 ) have been isolated in helium nanodroplets and probed with infrared
laser spectroscopy. Measurements are carried out in the high frequency OH/CH stretch region (2900-3600 cm−1 ) and in
the OOO symmetric and antisymmetric stretch region near 1050 cm−1 . Many of the observed bands exhibit rotational fine
structure, allowing for structural assignments via Stark spectroscopy. Rotationally resolved vibrational bands of the OH-O3
complex indicate a rather weak interaction, as the orbital angular momentum of the unpaired electron is unquenched and
remains strongly coupled to the OH bond axis.
RB09
SPECTROSCOPY OF THE CH3 -HCL COMPLEX IN HELIUM NANODROPLETS
15 min
11:06
CHRISTOPHER P. MORADI and GARY E. DOUBERLY, Department of Chemistry, University of Georgia, Athens, Georgia 30602-2556.
The CH3 -HCl van der Waals complex has been isolated in superfluid helium nanodroplets, and the infrared-active hydrogen stretching vibrations have been identified. A 153 cm−1 redshift of the HCl stretch is observed (relative to the HCl
monomer peak at 2905 cm−1 ), consistent with the predicted hydrogen bonding interaction between the two molecules.
The perpendicular CH stretching transitions originating from (N,K) = (0,0) and (1,1) are also observed, and simulations
indicate that the band origin is shifted by roughly 6 cm−1 relative to the band origin of methyl radical in helium dropletsa
(3160.9(1) cm−1 ). The barrier height to formation of CH4 + Cl from CH3 + HCl is only 1.5 kcal mol−1 with a 0 K reaction
exothermicity of about 1.2 kcal mol−1 .b The broad linewidth of the parallel transition, relative to the perpendicular transition, indicates that excitation of the HCl stretch may be lifetime broadened due to optical pumping of the weakly bound
complex over the barrier to form CH4 + Cl. Additionally, one of the HCl stretches due to CH3 -(HCl)2 has been identified
and lies approximately 27 cm−1 to the red of the “bound" stretch of the HCl dimer at 2852 cm−1 . The feasibility of an
IR-IR double resonance experiment to probe for the photo-induced formation of CH4 -Cl will be discussed.
a A.
b A.
M. Morrison, P. L. Raston, G. E. Douberly. J. Phys. Chem. A. 2013, in press.
J. Orr-Ewing, C. Murray. Int. Rev. Phys. Chem. 2004, 4, 435-482.
273
RB10
15 min 11:23
BIMOLECULAR PYROLYSIS REACTIONS STUDIED BY CHIRPED-PULSE MILLIMETER-WAVE SPECTROSCOPY
KIRILL PROZUMENT, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA
02139; ANGAYLE K. VASILIOU, Department of Chemistry and Biochemistry, University of Colorado at
Boulder, Boulder, CO 80309; RACHEL G. SHAVER, G. BARRATT PARK, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139; JOHN S. MUENTER, Department of Chemistry,
University of Rochester, Rochester, NY 14627; JOHN F. STANTON, Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, TX 78712; G. BARNEY ELLISON, Department of Chemistry
and Biochemistry, University of Colorado at Boulder, Boulder, CO 80309; ROBERT W. FIELD, Department
of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139.
The feasibility of using Chirped-Pulse Millimeter-Wave (CPmmW) spectroscopy for studies of pyrolysis reactions is
demonstrated. The molecules under investigation were mixed with a source of H-atoms (methyl nitrite) and put through a
heated silicon carbide micro-reactor (2 cm x 1 mm). More efficient paths of thermal cracking of (i) acetaldehyde and (ii)
acetone are demonstrated when using, as a catalyst, the free H-atoms released from methyl nitrite compared to cracking of
neat acetaldehyde or acetone. CPmmW spectra of (i) formaldehyde and (ii) acetaldehyde were observed, suggesting that
the following bimolecular reactions took place in the micro-reactor:
i) CH3 CHO + H → CH3 + CH2 O
ii) CH3 COCH3 + H → CH3 + CH3 CHO.
The vibrational population distributions (VPDs) of the formaldehyde and acetaldehyde products of the pyrolysis reactions
are measured using the broad bandwidth capability of the CPmmW technique. Although we found that the VPDs of the
molecules convey little information about the pyrolysis reaction transition state(s), they provide insight to the vibrational
collisional cooling mechanisms in different molecules. The relevance of the observed catalytic reactions to biomass decomposition is discussed and other bimolecular pyrolysis reactions are proposed for study by CPmmW spectroscopy. KP
thanks the Petroleum Research Fund for support of this work.
RB11
5 min 11:40
SLOW PHOTOELECTRON SPECTROSCOPY AND STATE-SELECTED UNIMOLECULAR DECOMPOSITION OF
IONIZED DNA BASES ANALOGUES
AHMED MAHJOUB and MAJDI HOCHLAF, Universite Paris-Est, Laboratoire Modelisation et Simulation
Multi Echelle, MSME UMR 8208 CNR, 77454 Marne la vallee (France); LIONEL POISSON, Laboratoire
Francis Perrin CNR- URA 2453, CEA –IRAMIS, 91192, Gif sur Yvette (France); GUSTAVO A. GARCIA and
LAURENT NAHON, Synchrotron SOLEIL, LOrme des Merisiers, Saint Aubin BP 48, 91193 (France).
We studied the single-photon ionization of gas-phase 2-Piperidone (DNA basis analogue) and of its dimer using vacuumultraviolet (VUV) synchrotron radiation coupled to a velocity map imaging electron/ion coincidence spectrometera. The
slow photoelectron spectrum (SPES) of the monomer is dominated by the vibrational transitions to the ground state. These
spectra are assigned with the help of theoretical calculations dealing with the equilibrium geometries, electronic-state
patterns and evolutions, harmonic and anharmonic wavenumbers. After its formation, dimer is subject of intramolecular
isomerization, H transfer and then unimolecular fragmentation processes.
The near threshold photofragmentation pattern of the cationic 2-Piperidone cation and its dimer has been recorded. The
experimental method yields the fragment intensity as a function of the internal energy deposited into the parent cation. In
parallel, ab initio studies on ionic and neutral fragmentation products have been performed with the aim of determining the
isomers of the ionic products observed experimentally as well as of their neutral counterparts.
a L.
Nahon, N. De Oliveria,J. F. Gil,B. Pilette,O. Marcouillé, B. La garde and F. Polack Journal of Synchrotron Radiation 19(4), 508-520; 2012
274
RB12
15 min 11:47
INSIGHTS ON HYDROGEN LIBERATION FROM WATER USING ANIONIC TRANSITION METAL OXIDE CLUSTERS: A COMBINED COMPUTATIONAL AND SPECTROSCOPIC STUDY
RAGHUNATH O. RAMABHADRAN, JENNIFFER E. MANN, SARAH. E. WALLER, DAVID W.
ROTHGEB, CAROLINE C. JARROLD, KRISHNAN RAGHAVACHARI, DEPARTMENT OF CHEMISTRY,
INDIANA UNIVERSITY, BLOOMINGTON, IN-47405.
Transition Metal Oxides (TMOs) offer widespread applications in catalysis and the generation of alternate sources of
energy. Cluster models are useful to model the defect sites in these TMO surfaces which are responsible for their catalytic
activities. In this combined computational (DFT) and spectroscopic (PES/MS) study, we present the interesting features in
the chemical reactions of molybdenum oxide and tungsten oxide clusters with water. The results obtained provide valuable
insights on the roles played by differing metal-oxygen bond strengths, the initial electrostatic complex formed and the
geometric factors involved in the liberation of hydrogen gas from water.
275
RC. MICROWAVE
Room: 1000MCPHERSON LAB
Chair: ROBERT BOHN, University of Connecticut, Storrs, CT
RC01
THE ROTATIONAL SPECTRUM OF RUTHENIUM MONOCARBIDE USING PPMODRa
15 min 8:30
AZ 85287; ALLAN G. ADAM, Center for Lasers, Atomic and Molecular Sciences and Physics Department,
University of New Brunswick, Fredericton, NB Canada E3B 5A3.
Predicting the properties of simple second row transition metal containing molecules is surprisingly challenging because
of the significant relativistic effects as well as the large dynamic electron correlation. Assessing the multitude of computational methodologies being developed for addressing these effects is most readily achieved by comparing of experimentally derived and predicted hyperfine parameters . The interaction between the nuclear electric quadrupole moment and
the electric-field gradient at the site of the same nucleus is particularly useful for testing various relativistic effectsb . As
part of our continuing study of RuCc , here we report on the experimental determination of the electric quadrupole coupling
parameter for 101 RuC from the analysis of the pure rotational spectrum. The J= 0→1 and J=1→2 transitions for ground
state (X1 Σ+ ) 101 RuC and 102 RuC were recorded using the separated field pump/probe microwave optical double resonance
technique.
a Funded
by DoE-BES
L; Stopkowicz, S; Stanton, J.F., Gauss, J,; J. Chem. Phys, 137, 224302, 2012.
c Steimle, T.C., Virgo, W.L., Brown, J.M.; J. Chem. Phys, 118, 2620, 2003.
b Cheng,
RC02
15 min 8:47
PURE ROTATIONAL SPECTRA OF THE REACTION PRODUCTS OF LASER ABLATED THORIUM METAL AND
OXYGEN MOLECULES ENTRAINED WITHIN SUPERSONIC EXPANSIONS OF NOBLE GASES
B. E. LONG, Department of Chemistry, Wesleyan University, 52 Lawn Avenue, Middletown, Connecticut,
06459; S. A. COOKE, School of Natural and Social Sciences, Purchase College SUNY, 735 Anderson Hill
Road, Purchase, NY 10577, USA.
Thorium metal has been laser ablated in the presence of pure oxygen entrained in
high pressure argon. The products of the ablation event have been supersonically expanded into the Fabry-Pérot cavity of a time-domain microwave spectrometer. New
measurements have been performed on thorium monoxide, where the J = 1 ← 0
transition has been recorded in the v = 8, 9, and 10 vibrational levels. Further to
this, a thorium-dependent spectral transition has been observed at 19251.8740(10)
MHz. The carrier of this signal is to be determined, however, it requires an oxygen
concentration of 0.1 % which is significantly higher than the optimal oxygen concentration required for observation of the thorium monoxide transitions. It is postulated
that the presently unidentified thorium-containing compound is ThO2 which has C2 v
symmetry. Progress on the measurement of this spectra, together with other thorium
experiments and supporting quantum chemical calculations, will be presented.
276
RC03
DETECTION OF THE ROTATIONAL SPECTRUM OF SULFOXYLIC ACID (HOSOH)
15 min 9:04
KYLE N. CRABTREE, OSCAR MARTINEZ, JR., LOU BARREAUa and MICHAEL C. McCARTHY,
Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, 02138; SVEN THORWIRTH, I. Physikalisches Institut, Universität zu Köln, 50937 Köln, Germany.
Sulfoxylic acid (HOSOH) is a chemical intermediate that falls roughly midway in the oxidation states of sulfur, between
its highly reduced (H2 S) and oxidixed (H2 SO4 ) forms. It is likely formed during atmospheric oxidation of anthropogenic
and natural sulfur emissions, and might also be produced by UV processing of circumstellar ices. Despite considerable
theoretical work, no gas-phase spectra of sulfoxylic acid or any of its structural isomers have previously been observed.
We report the detection of the rotational spectra of the C2 and Cs rotamers of HOSOH using a combination of Fourier
transform microwave spectroscopy and microwave-microwave double resonance techniques, guided by new high-level
quantum chemical calculations of their structures. The present work enables radioastronomical searches for these species,
and also lays the groundwork for further chemical studies of its gas-phase formation and spectroscopic studies of other
H2 SO2 isomers.
a Present
address: École Normale Supérieure de Cachan, 94235 Cachan Cedex, France
RC04
15 min 9:21
GLOBAL ANALYSIS OF BROADBAND ROTATION AND VIBRATION-ROTATION SPECTRA OF SULFUR DICYANIDE
Poland; MANFRED WINNEWISSSER, BRENDA P. WINNEWISSER, FRANK C. DE LUCIA, Department
of Physics, The Ohio State University, Columbus, OH 43210, USA; DENNIS W. TOKARYK, Department of
Physics and Centre for Laser, Atomic, and Molecular Sciences, University of New Brunswick, P.O.Box. 4400,
New Brunswick E3B 5A3, Canada; BRANT E. BILLINGHURST, Canadian Light Source Inc., University of
Saskatchewan, 101 Perimeter Road, Saskatoon, Saskatchewan S7N 0X4, Canada.
The successful analysis of the quantum monodromy induced features in the rotational spectrum of the NCNCS moleculea
prompted a quest for similar behaviour in its vibration-rotation spectrum and several high-resolution FT-IR spectra were
recorded on the IFS125HR interferometer at the Canadian Light Source.b The sulfur dicyanide, S(CN)2 , molecule is
a precursor to NCNCS and the analysis of its spectrum proved to be a prerequisite to a search for the elusive NCNCS
transitions. The CLS spectra provided the opportunity to augment the previous extensive analysis of the FASSST rotational
spectrum of S(CN)2 c with vibration-rotation data, in particular from the ν4 fundamental at 121 cm−1 and its related hotband series. A global fit of the two data sets allowed retaining the detailed analysis of the previously reported perturbations
in the 3ν4 triad and 4ν4 tetrad of states, while allowing for determination of precise energies of all low-lying vibrational
states of S(CN)2 . In this way we have determined wavenumbers for five lowest fundamentals of this experimentally
difficult molecule and obtained an extensive set of benchmark data for calibration of anharmonic force field calculations
of such quantities as the vibration-rotation changes in rotational constants, and anharmonicity coefficients. Comparisons
with results of several such calculations are presented.
a B.P.Winnewisser,
et al., Phys. Chem. Chem. Phys. 12, 8158 (2010).
et al., 67th OSU Symposium on Molecular Spectroscopy, The Ohio State University, Ohio 2012, TF-01.
c Z.Kisiel et al., J. Mol. Spectrosc. 246, 39 (2007).
b M.Winnewisser
277
RC05
15 min 9:38
CONTINUATION OF THE PURSUIT OF THE FAR-INFRARED SPECTRUM OF NCNCS, AT THE CANADIAN
LIGHT SOURCE
MANFRED WINNEWISSER, BRENDA P. WINNEWISSER,
FRANK C. DE LUCIA, Department of Physics, The Ohio State University, Columbus Ohio, 43210-1106, USA; DENNIS W. TOKARYK, STEPHEN C. ROSS, Department of Physics and Centre for Laser, Atomic, and
Molecular Sciences, University of New Brunswick, P.O. Box 4400, Fredericton NB E3B 5A3, Canada;
BRANT E. BILLINGHURST, Canadian Light Source Inc., University of Saskatchewan, 101 Perimeter Road,
Saskatoon, Saskatchewan S7N 0X4,Canada.
The molecule cyanogen iso-thiocyanate, NCNCS, has proved to be the most revealing model system for studying the effects
of molecular quantum monodromya. In two previous measuring campaigns in May 2011 and May 2012 at the Canadian
Light Source (CLS) at the University of Saskatchewan we have obtained a rich collection of high-resolution infrared band
systems for both S(CN)2 and its isomer NCNCS which is our target molecule. We found experimentally that NCNCS is the
more stable isomer. Some results for S(CN)2 are reported in the adjacent talk in this session. However, the isomerization
between S(CN)2 and NCNCS and other reaction products make the attainment of a pure sample of NCNCS difficult and
time consuming. We have not yet obtained a satisfactory high-resolution recording of the quasi-linear bending mode in the
far infrared in the two allotments of beam time so far available to us. Our theoretical preparations for the project include
recent refinements of predictions of intensities in the low-lying bending mode band system, which will be shown. The
experimental aspects of obtaining an optimal sample of NCNCS in order to observe the rotational resolved spectrum in the
CLS campaign scheduled for May 2013, and an initial report of the results, will also be discussed.
a B.
P. Winnewisser, M. Winnewisser, I. R. Medvedev, F. C. De Lucia, S. C. Ross and J. Koput, Phys. Chem. Chem. Phys., 12, 8158 (2010)
RC06
15 min 9:55
TERAHERTZ SPECTROSCOPY OF CaH (X Σ ), MgH (X Σ ), AND ZnH (X Σ ) : EXTREME HYDRIDE SYNTHESIS
2
+
2
+
2
+
MATTHEW P. BUCCHINO, Department of Chemistry and Biochemistry, University of Arizona, Tucson, Arizona 85721; and LUCY M. ZIURYS, Department of Chemistry and Biochemistry, Department of Astronomy,
and Steward Observatory, University of Arizona, Tucson, Arizona 85721.
Sub-millimeter spectra of CaH (X2 Σ+ ), MgH (X2 Σ+ ), and ZnH (X2 Σ+ ) have been measured in the sub-mm/THz regime
(500−805 GHz) using direct-absorption methods. All species were produced by the reaction of metal vapor with H2 under
DC discharge in a Broida-type oven. Because of efficient molecule production, spectra of 26 MgH, 66 ZnH, 68 ZnH and
70
ZnH could be recorded in their natural abundance as well, with high signal-to-noise. Additionally, the N = 0 → 1 and
N = 1 → 2 transitions of 25 MgH and 67 ZnH were measured. Fermi contact, dipolar, and quadrupole constants for the
25
Mg and 67 Zn nuclei have been accurately determined for the first time in the gas phase, and are in good agreement
with previous ESR studies. The hyperfine constants suggest a substantial amount of covalent character is present in metal
hydrides.
Intermission
278
RC07
15 min 10:30
THE MILLIMETER DIRECT ABSORPTION AND FOURIER TRANSFORM MICROWAVE SPECTRUM OF VANADIUM SULFIDE (X4 Σ− )
Tucson, 85721.
The pure rotational spectrum of VS (X4 Σ− ) has been measured with Fourier transform microwave (FTMW) and
millimeter-wave direct absorption methods in the frequency range of 5-40 GHz and 210-315 GHz. Discharge assisted
laser ablation (DALAS) of a vanadium rod in presence of H2 S gas was used to synthesize the radical in the microwave
region. In the millimeter-wave range, the species was produced from the mixture of CS2 and VCl4 vapor in a DC discharge.
The hyperfine structure was resolved and accurate fine and hyperfine parameters were obtained. Insights into the bonding character can be gleamed from the hyperfine constants, and an estimate of the position of two low-lying interacting
electronic states can be obtain from the fine structure parameters. Details of these results will be discussed.
RC08
15 min
10:47
MILLIMETER AND SUB-MILLIMETER SPECTROSCOPY OF CRCCH (X Σ )
6
+
JIE MIN, LUCY. M. ZIURYS, Department of Chemistry and Biochemistry, Department of Astronomy, and
Steward Observatory, University of Arizona, Tucson, AZ 85721.
The pure rotational spectrum of CrCCH has been measured using millimeter/sub-millimeter direct absorption methods in
the frequency range of 445-485 GHz. The molecule was created in an AC discharge of Cr(CO)6 , acetylene and argon.
Six rotational transitions were measured. The spectra clearly indicate that the electronic ground state is a sextet. Spectra
of CrCCD have also been recorded using the mixture of Cr(CO)6 , deuterated acetylene and argon in an AC discharge.
The data were fit with a Hund’s case (b) Hamiltonian and rotational, spin-rotation and spin-spin parameters have been
determined. The structure has been calculated based on the rotational constants.
RC09
15 min
CHARACTERIZATION OF SILICON SULFIDES BY CHIRPED-PULSE ROTATIONAL SPECTROSCOPY
11:04
Chirped-pulse Fourier transform microwave spectroscopy is used to characterize the electrical discharge products that
are formed in a supersonic molecular beam through a dilute gas mixture of silane and hydrogen sulfide. The spectrum
between 6 and 18 GHz is dominated by SiS: more than 175 transitions have been assigned to either its isotopic species, its
vibrationally excited states, or both, on the basis of previous cavity measurements. Owing to the flat instrument response
function and extensive vibrational excitation that has been observed, it is possible to derive a precise vibrational temperature
for SiS, and determine the relative abundances of SiS, HSiS, and H2 SiS. Although rotational lines from more than 15 other
silicon or sulfur molecules have been identified in the same discharge, more than 50% of lines that have been detected with
a signal-to-noise ratio of three or greater are presently unassigned. Attempts to assign these many remaining lines, and
efforts to benchmark the performance of our spectrometer will be highlighted as well.
279
RC10
15 min 11:21
DETECTION OF TWO HIGHLY-STABLE SILICON NITRIDES BY CHIRPED-PULSE ROTATIONAL SPECTROSCOPY: HSiNSi and SiH3 NSi
By means of chirped-pulse and cavity Fourier transform microwave spectroscopy of a supersonic molecular beam, the
rotational spectra of two new silicon nitrides, HSiNSi and SiH3 NSi, have been detected in a discharge through dilute gas
mixtures of either molecular nitrogen or ammonia and silane. Both molecules appear to be highly stable: they are by far
the most readily observed silicon-nitrogen containing molecules in the 6-20 GHz frequency range, even though neither has
apparently been the subject of prior experimental or theoretical studies. Density-functional calculations performed here
confirm that both structures are deep minima on their respective potential energy surfaces, and each possesses a sizable
dipole moment. Owing to their high abundance, in excess of 1012 molecules/gas pulse, extensive isotopic spectroscopy
has been undertaken for both. Detection of other silicon-nitride clusters in the transition region from atomic constituents
to Si3 N4 by similar means may be promising.
RC11
FOURIER-TRANSFORM MICROWAVE SPECTROSCOPY OF HCCNSi AND NCNSi
15 min
11:38
S. THORWIRTH, I. Physikalisches Institut, Universität zu Köln, 50937 Köln, Germany; R. I. KAISER, Department of Chemistry, University of Hawaii at Manoa, Honolulu, HI 96822, U.S.A.; M. C. MCCARTHY, K.
N. CRABTREE, O. MARTINEZ, JR., Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138, U.S.A. and School of Engineering and Applied Sciences, Harvard University, 29 Oxford
Street, Cambridge, MA 02138, U.S.A.
By means of Fourier transform microwave spectroscopy of a supersonic jet, the pure rotational spectra of the silicon-bearing
chain molecules silaisocyanoacetylene, HCCNSi, and cyanosilaisocyanide, NCNSi, have been studied for the first time.
The molecules were observed in low-current dc discharges through appropriate gas mixtures comprising CH3 CN/SiH4
and cyanogen/SiH4 heavily diluted in neon. Spectroscopic searches and identification were based on predictions from
high-level quantum-chemical calculations at the CCSD(T) level of theory in combination with large basis sets. Excellent
agreement between experimental and calculated molecular parameters is found. In addition to the parent isotopic species,
rotational lines of rare isotopologs were also observed.
Because of the close relationship of these two species to known astronomical molecules and due to their sizable dipole
moments of µ = 1.4 D (HCCNSi) and µ = 5.4 D (NCNSi) both are plausible targets for future astronomical searches
using large radio telescopes.
280
RC12
15 min 11:55
SUBSTITUTION STRUCTURES OF MULTIPLE SILICON-CONTAINING SPECIES BY CHIRPED PULSE FTMW
SPECTROSCOPY
NATHAN A. SEIFERT, SIMON LOBSIGER, BROOKS H. PATE, Department of Chemistry, University of
Virginia, McCormick Rd., Charlottesville, VA 22904-4319; GAMIL A. GUIRGIS, JASON S. OVERBY,
Department of Chemistry & Biochemistry, College of Charleston, Charleston, SC 29424 USA; JAMES R.
DURIG, Department of Chemistry, University of Missouri-Kansas City, Kansas City, MO 64110 USA.
The structures of CH3 SiHF-NCO, 1-X-silacyclopropane (X = cyano, isocyanato), 1,1,3,3-tetrafluoro-1,3disilacyclopentane and its hydrogen analogue (1,3-disilacyclopentane), and 1-isocyanato-silacyclohexane have been
studied by chirped pulse FTMW spectroscopy in the 6-18 GHz band. Multiple conformers for some of the species were
also detected: anti and gauche for both silacyclopropyl species, and axial and equatorial for the silacyclohexane. Heavy
atom substitution structures were determined, with all possible single 13 C, 29 Si/30 Si and most 15 N isotopologues assigned
in natural abundance. Nitrogen hyperfine and distortion parameters for all species have been determined, and the barrier
for methyl internal rotation for CH3 SiHF-NCO has been determined as 481(20) cm−1 , close to the B3LYP/6-311++g(d,p)
barrier of 450 cm−1 . A summary of the microwave and structural results for the aforementioned molecules will be
presented. In addition, emphasis will be placed on the use of previously discussedab automated fitting techniques as a
means of efficient and fast assignment of isotopologues in spectra with increasingly large line densities.
a A. L. Steber, J. L. Neill, M. T. Muckle, B. H. Pate, D. F. Plusquellic, V. Lattanzi, S. Spezzano, M. C. McCarthy. 65th OSU Int. Symp. On Mol.
Spectrosc., Columbus, OH, 2010, TC10.
b E. B. Kent, M. N. McCabe, M. A. Phillips, B. P. Gordon, S. T. Shipman. 66th OSU Int. Symp. On Mol. Spectrosc., Columbus, OH, 2011, RH01.
281
RD. ELECTRONIC
Chair: ALLAN S. C. CHEUNG, University of Hong Kong, Hong Kong
RD01
METHODS FOR MANIPULATING CaF USING OPTICAL POLYCHROMATIC FORCES
15 min 8:30
EDWARD E. EYLER, SCOTT E. GALICA, and LELAND M. ALDRIDGE, Department of Physics, University of Connecticut, Storrs, CT 06269, USA.
We are undertaking theoretical and experimental studies of laser deceleration and cooling of molecules using coherent
multi-frequency optical forces. A primary objective is to reduce radiative loss into dark states when a pure two-level
cycling transition is unavailable. The optical bichromatic force (BCF) can multiply the available velocity change for a
given number of radiative cycles, by employing alternating cycles of excitation and stimulated emission from opposing
directions. Tests in atomic helium show that when the BCF is combined with frequency chirping, very large decelerations
are achieved.a We report numerical studies of variations intended to further optimize deceleration, including a 4-color
version. We describe progress on experimental tests using the 531 nm B 2 Σ+ ↔ X 2 Σ+ transition in CaF.
We also describe low-cost lasers and electronics developed for these experiments. Several versatile new instruments are
based on 32-bit microcontrollers, interfaced to an Android tablet that provides a touch-screen graphical interface. These
include a timing/ramp generator, a PZT driver, a temperature controller, and even a phase-synchronized dual 35-4000 MHz
rf synthesizer that fits on a 2 41 ” × 4 43 " board. This research is supported by the National Science Foundation.
a M.A.
Chieda and E.E. Eyler, Phys. Rev. A 86, 053415 (2012); also Phys. Rev. A 84, 063401 (2011).
RD02
15 min 8:47
NEW LINE LISTS INCLUDING INTENSITIES FOR THE C2 SWAN SYSTEM (d Πg -a Πu ), C2 SINGLET SYSTEMS
AND ROVIBRATIONAL TRANSITIONS WITHIN THE NH X3 Σ− GROUND STATE.
3
3
J. S. A. BROOKE, Department of Chemistry, University of York, York, UK; P. F. BERNATH, Department
of Chemistry & Biochemistry, Old Dominion University, Norfolk, VA, USA; C. M. WESTERN, School of
Chemistry, University of Bristol, Bristol, UK; T. W. SCHMIDT and G. B. BACSKAY, School of Chemistry, The
University of Sydney, New South Wales, Australia; M. C. VAN HEMERT, Department of Chemistry, Gorlaeus
Laboratories, Leiden University, The Netherlands; G. C. GROENENBOOM, Theoretical Chemistry, Institute
for Molecules and Materials (IMM), Radboud University Nijmegen, Nijmegen, The Netherlands.
Line lists including both positions and absolute intensities are required by those who wish to calculate abundances from
spectroscopic observations. New line lists for the diatomic molecules C2 and NH are presented.
Line strengths for the C2 Swan system (d3 Πg -a3 Πu ) have been calculated for vibrational bands with v′ =0-10 and v′′ =0-9,
and J values up to J=34-96, based on previous observations in 36 vibrational bands. Line positions from several sources
were combined with the results from recent deperturbation studies of the v′ =4 and v′ =6 levels, to provide updated molecular
constants. The line strengths are based on a recent ab initio calculation of the transition dipole moment function. Einstein
A coefficients and f -values were also calculated for the vibrational bands of the Swan system. A line list has been made
available, including observed and calculated line positions, Einstein A coefficients and oscillator strengths (f -values). This
list will be useful for astronomers, combustion scientists and materials scientists who utilize C2 Swan spectra. Similar
work is being carried out for a number of singlet systems of C2 , in which a single global fit of positions will be performed
and intensities calculated.
For NH, a line list is being created for the infrared transitions within the X3 Σ− ground state, including previous observations of rotational lines within v=0-2, and rovibrational lines of the ∆v=1 sequence up to v′ =6. The intensity calculations
use a recently calculated dipole moment function which has been used to calculate the lifetime of the v=1 level, but was
unpublished. A line list like that for the C2 Swan system will be made available, which will be useful for astronomers
investigating NH and nitrogen abundance in cool objects.
282
RD03
15 min 9:04
MEASUREMENT OF ABSOLUTE HYDROXYL RADICAL CONCENTRATION IN LEAN FUEL-AIR MIXTURES
EXCITED BY NANOSECOND PULSED DISCHARGEa .
Z. YIN, W. R. LEMPERT, I. V. ADAMOVICH, The Ohio State University, Dept. of Mechanical and
Aerospace Engineering, Columbus, OH 43210.
The focus in plasma assisted combustion research has been on the evaluation of conventional plasma/combustion mechanisms in predicting oxidation and ignition processes initiated and/or sustained by non-equilibrium, nanosecond discharges.
Accurate quantitative data such as temperature and species concentration are needed for assessing and improving numerical modeling. As an important intermediate species, the concentration of hydroxyl radical (OH) is very sensitive to the
combustion environment (e.g., temperature, equivalence ratio), and therefore is of great interest to kinetic study.
In this work, Laser-Induced Fluorescence (LIF) was used for time-resolved temperature and OH number density measurements in lean H2 -, CH4 -, C2 H4 −, and C3 H8 − air mixtures in a plasma flow reactor inside a tube furnace. The premixed
fuel-air flow in the reactor, initially at T0 =500 K and P=100 torr, was excited by a burst of repetitive nanosecond electric pulses in a dielectric-barrier plane-to-plane geometry (∼28 kV peak voltage and ∼5 nsec pulse width, estimated 1.25
mJ/pulse coupled energy). Laser was timed to probe after the discharge burst was over to avoid strong plasma emission
interference. Relative fluorescence signal was put on an absolute scale by calibrating against Rayleigh scattering signal in
the same flow reactor. Experimental results were compared to predictions from a 0-D plasma/combustion chemistry model
employing several well-established combustion mechanisms. 2-D temperature and OH concentration distributions in the
discharge volume were obtained by planar LIF and was used to quantitatively evaluate plasma uniformity in the reactor.
These results were used to determine the validity of the 0-D model.
a Funded
by AFOSR MURI for plasma assisted combustion research grant
RD04
15 min 9:21
LASER INDUCED FLUORESCENCE SPECTROSCOPY OF JET COOLED SiCN : ROTATIONAL ANALYSIS OF
THE HOT BANDS
We have generated SiCN in supersonic free jet expansions, and observed the laser induced fluorescence ( LIF ) of the
vibrationally hot bands of the Ã 2 ∆ – X̃ 2 Π transition. We have measured dispersed fluorescence ( DF ) spectra from
the single vibronic levels ( SVL’s ), Ã (011 0) 2 Φ and 2 Π, and rotationally resolved LIF excitation spectra of the two hot
bands, Ã (011 0) 2 Φ – X̃ (011 0) 2 ∆ and Ã (011 0) 2 Π – X̃ (011 0) 2 Σ(−) . The rotational energy levels were reasonably
analyzed as those of the 2 K ′ – 2 K ′′ transitions, but their line intensities calculated from the Hönl-London factors derived
in the intermediate case between Hund’s case (a) and (b) could not reproduce the observed spectra. The Hönl-London
factors derived in the 2 Λ′ – 2 Λ′′ ( 2 ∆ – 2 Π ) transition reasonably reproduced the spectra. It indicates that coupling
between the electronic orbital and vibrational angular momenta is weak in the SiCN 2 ∆ – 2 Π system, and a basis set of
|Λ v2 l Σ; J P MJ i, so-called ”l-basis", better describes the system than that of |Λ v2 K Σ; J P MJ i.
283
RD05
THE ELECTRIC DIPOLE MOMENT OF IRIDIUM MONOSILICIDE, IrSi
15 min 9:38
ANH LE AND TIMOTHY C. STEIMLE, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ 85287; LAN CHENG AND JOHN F. STANTON, The University of Texas at Austin, Austin,
TX 78712-0165.
The optical spectrum of iridium monosilicide (IrSi) was recently observed using REMPI spectroscopy in the range 17200 to
23850 cm−1a . The observation was supported by an ab initio calculation which predicted a X2 ∆5/2 state. Here, we report
on the analysis of the optical Stark effect for the X2 ∆5/2 and [16.0]1.5 (v=6) states. The (6,0)[16.0]1.5 - X2 ∆5/2 and the
(7,0)[16.0]3.5- X2 ∆5/2 bands of IrSi have been recorded using high-resolution laser-induced fluorescence spectroscopy.
The observed optical Stark shifts for the 193 IrSi and 191 IrSi isotopologues were analyzed to produce the electric dipole
moments of -0.4139(64)D and 0.7821(63)D for the X2 ∆5/2 and [16.0]1.5 (v=6) states, respectively. The negative sign
of electric dipole moment of the X2 ∆5/2 state is supported by high-level quantum-chemical calculations employing allelectron scalar-relativistic CCSD(T) method augmented with spin-orbit corrections as well as corrections due to full triple
excitations. In particular, electron-correlation effects have been shown to be essential in the prediction of the negative sign
of the dipole moment. A comparison with other iridium containing molecules will be made.
a Maria A. Garcia, Carolin Vietz, Fernando Ruipérez, Michael D. Morse, and Ivan Infante, Kimika Fakultatea, Euskal Herriko. J. Chem. Phys.,
(submitted)
RD06
15 min 9:55
TRIPLE-SINGLET MIXING in Si3 : the 1
3
A′′1
-ã
3
A′2
TRANSITION
a
RUOHAN ZHANG, AND TIMOTHY C. STEIMLE, Department of Chemistry and Biochemistry, Arizona
State University, Tempe, AZ 85287.
The electronic spectrum of the triplet states of the D3h isomer of Si3 recorded using both mass selected REMPI and LIF
spectroscopy was recently reportedb. In that same study the dispersed laser induced fluorescence (DLIF) spectra resulting
from excitation of various bands in the visible range were recorded. The DLIF spectra exhibited a progression with a
505 cm−1 spacing, which was assign to the breathing mode of the D3h , equilateral triangle, Si3 molecule. In addition,
and quite unexpectedly, the DLIF spectra exhibited a progression having a spacing of 173 cm−1 . This progression was
tentatively assigned to transition involving the bending mode of the 1 A1 state of the C2v isomer. A possible explanation
for the observation of transitions in the singlet manifold is that upon laser excitation in the D3h triplet manifold there is
rapid intersystem crossing to the singlet manifold followed by fluorescence to the ground state of C2v isomer. Here we
address the issue of possible intersystem crossing by recording the excitation on DLIF spectra in the present of a static
magnetic field. Magnetic fields are known to enhance the singlet-triple mixingc. Si3 was produced using a supersonic
pulsed discharge source (900 V, 20 µs, 6kΩ) with a 1% SiH4 in argon mixture. Magnetic fields of approximately 500
and 950 Gauss were applied. We will report the interpretation of the magnetic field induced changes to the LIF and DLIF
spectra and the implications for the singlet-triple mixing process.
a Funded
by the NSF
X. Zhuang, V. Gupta, R. Nagarajan, R. C. Fortenberry, J. P. Maier, T. C. Steimle, J. F. Stanton, M. C. McCarthy; J. Chem. Phys., 136(19),
194307, (2004).
c V. I. Makarov, I. V. Khmelinskii; Advances in Chemical Phisics, Volume 118, 45-98, (2001).
b N. J. Reilly,
284
RD07
MULTIPLEXED MODR WITH APPLICATIONS TO THE ELECTRONIC SPECTRUM OF SO2
15 min
10:12
G. BARRATT PARK and ROBERT W. FIELD, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139; ANDREW R. WHITEHILL and SHUHEI ONO, Department of Earth, Atmospheric, and Planetary Sciences, Massachusetts Institute of Technology, Cambridge, MA 02139.
Application of broadband chirped-pulse technology to Microwave-Optical Double Resonance (MODR) allows simultaneous acquisition of MODR spectra for multiple microwave transitions. This new multiplexed implementation of MODR
is capable of resolving and rotationally assigning complicated and congested spectral regions with a single laser scan and
serves as a powerful complement to Laser Induced Fluorescence. Applications to the spectroscopy of SO2 will be presented. The photolysis of SO2 has been the subject of extensive study and has been invoked as an important mechanism for
mass-independent fractionation of sulfur isotopes in the Precambrian atmosphere. Multiplexed MODR has enabled new
assignments in congested and perturbed regions of the spectrum that were previously unassignable.
Intermission
RD08
15 min
10:45
SPECTROSCOPY OF THE NO-Ar COMPLEX IN THE VICINITY OF THE 3p ← X Π TRANSITIONS IN NITRIC
OXIDE
2
JOE P. HARRIS, TIMOTHY G. WRIGHT, ADRIAN M. GARDNER, ANNA ANDREJEVA,
NICHOLAS A. BESLEY and OLGA V. ERSHOVA, School of Chemistry, University Park, University
of Nottingham, NG7 2RD, United Kingdom; JACEK KLOS, Department of Chemistry, University of
Maryland, College Park, MD 20742.
Spectra of the NO-Ar complex have been recorded using REMPI spectroscopy in the region corresponding to transitions
to the 3p Rydberg states in uncomplexed NO. Additionally, spectra have been simulated using ab initio techniques with
the aim of better understanding this region, as previous favourable results have been obtained using a similar approach for
the 3s Rydberg statea . Excellent agreement with the REMPI spectra is seen for the 3pπ state simulation. Results on the
3pσ state will be discussed, along with extension to other NO-Rare Gas complexes.
a J.
Klos, M. H. Alexander, R. Hernández-Lamoneda and T. G. Wright J. Chem. Phys., 129, 244303 (2008)
RD09
15 min
AN INTRODUCTION TO HIGH RESOLUTION COHERENT MULTIDIMENSIONAL SPECTROSCOPY
11:02
PETER C. CHEN, THRESA A. WELLS, and ZURI R. HOUSE, Spelman College Chemistry Department,
High resolution coherent multidimensional spectroscopy is a technique that can be used to analyze and assign peaks for
molecules that have resisted spectral analysis. Molecules that yield heavily congested and seemingly patternless spectra using conventional methods can yield 2D spectra that have recognizable patterns. The off-diagonal region of the coherent 2D
plot shows only cross-peaks that are related by rotational selection rules. The resulting patterns facilitate peak assignment
if they are sufficiently resolved. For systems that are not well-resolved, coherent 3D spectra may be generated to further
improve resolution and provide selectivity. This presentation will provide an introduction to high resolution coherent 2D
and 3D spectroscopies.
285
RD10
15 min 11:19
STRATEGIES FOR INTERPRETING HIGH RESOLUTION COHERENT MULTIDIMENSIONAL SPECTRA
THRESA A. WELLS, ZURI R. HOUSE, and PETER C. CHEN, Spelman College Chemistry Department, 350
Spelman Lane, Atlanta, GA 30314; BENJAMIN R. STRANGFELD, Department of Chemistry and Chemical
Biology, Georgia Institute of Technology, Atlanta, GA 30332.
The electronic spectra of certain molecules can be very complex and consist of a high density of peaks. The high density
of peaks results in severe spectral congestion, making conventional data analysis techniques extremely difficult to use.
One solution to this problem is to use high resolution coherent 2D spectroscopy (HRC2DS), which can improve resolution
and sort peaks into recognizable clusters. This technique requires new data analysis techniques to accurately assign peaks.
Even though HRC2DS can improve spectral resolution, some regions of the spectra may still remain congested. The ability
to solve this problem using even higher dimensional techniques (e.g., high resolution coherent 3D spectroscopy) with 3D
pattern recognition and data analysis techniques will be discussed.
RD11
HIGH RESOLUTION COHERENT 3D SPECTROSCOPY OF BROMINE
15 min
11:36
BENJAMIN R. STRANGFELD, Department of Chemistry and Chemical Biology, Georgia Institute of Technology, Atlanta, GA 30332; THRESA A. WELLS, ZURI R. HOUSE, and PETER C. CHEN, Spelman College
Chemistry Department, 350 Spelman Lane, Atlanta, GA 30314.
The high resolution gas phase electronic spectrum of bromine is rather congested due to many overlapping vibrational and
rotational transitions with similar transition frequencies, and also due to isotopomeric effects. Expansion into the second
dimension will remove some of this congestion; however through the implementation of High Resolution Coherent 3D
Spectroscopy, the density of peaks is further reduced by at least two orders of magnitude. This allows for the selective
examination of a small number of spatially resolved multidimensional bands, separated by vibrational quantum number
and by isotopomer, which facilitates the fitting of many rovibrational peaks in bromine. The ability to derive information
about the molecular constants for the electronic states involved will be discussed.
RD12
HIGH RESOLUTION COHERENT THREE-DIMENSIONAL SPECTROSCOPY OF IODINE
10 min
11:53
ZURI R. HOUSE, THRESA A. WELLS, and PETER C. CHEN, Spelman College Chemistry Department,
The heavy congestion found in many one-dimensional spectra can make it difficult to study many transitions. A new
coherent three-dimensional spectroscopic technique has been developed to eliminate the kind of congestion commonly
seen in high resolution electronic spectra. The molecule used for this test was Iodine. A well-characterized transition (X
to B) was used to determine which four wave mixing process or processes were responsible for the peaks in the resulting
multidimensional spectrum. The resolution of several peaks that overlap in a coherent 2D spectrum can be accomplished by
using a higher dimensional (3D) spectroscopic method. This talk will discuss strategies for finding spectroscopic constants
using this high resolution coherent 3D spectroscopic method.
286
RE. MINI-SYMPOSIUM: SPECTROSCOPY OF PLANETARY
ATMOSPHERES
Chair: VINCENT BOUDON, CNRS/Université de Bourgogne, Dijon, France
RE01
INVITED TALK
30 min 8:30
SATELLITE REMOTE SENSING OF THE REACTIVE LOWER ATMOSPHERE USING MEDIUM RESOLUTION
INFRARED MEASUREMENTS: HIGHLIGHTS FROM IASI MISSION
P.F. COHEUR, Atmospheric Spectroscopy / Quantum Chemistry and Photophysics, Université Libre de Bruxelles CP160/09, Brussels, Belgium.
Human activities have significantly altered the equilibrium of the Earth atmosphere. If the steady increase in the
concentration of greenhouse gases has attracted most of the attention, it is important as well to monitor the evolution of
our “reactive atmosphere”, as shorter-lived atmospheric species impact human health and ecosystems directly (e.g. local
air quality) or indirectly (e.g. chemistry-climate interactions), through poorly known and quantified processes. Optical
instruments on board satellites, and especially those operating in the infrared with sufficient spectral resolution, provide
unique opportunity for measuring reactive trace gases in the troposphere and the stratosphere on various scales. The
presentation focuses on the measurements of the Infrared Atmospheric Sounding Interferometer IASI onboard Metop
satellites.
IASI makes global measurements of the Earth atmosphere in a nadir view, i.e. looking downward at the terrestrial radiation,
with a horizontal resolution of a few hundreds km2 . It provides more than 106 radiance spectra daily, which cover the
infrared range between 645 and 2760 cm−1 at medium spectral resolution (0.5 cm−1 apodized) and low noise. This,
coupled to the exceptional sampling performances of IASI, made breakthroughs in the fields of atmospheric spectroscopy
and chemistry. In this talk, we will shortly describe IASI instrument and its spectral measurements, as well as the radiative
transfer model and retrieval scheme set up for near-real-time processing. We will review the principal accomplishments
of IASI in probing the reactive atmosphere by measuring simultaneously the concentrations of about 25 trace species with
short (e.g. NH3 , SO2 ) to medium (e.g. O3 , CO) residence time, and from the local emission hotspot to the planetary scale.
We will put emphasis on the challenging measurements of the polluted planetary boundary layer and will also show a series
of focused results on pollution outflow, transport and in-plume chemistry; possibly global budgets. We will briefly expose
how five-years of global measurements can contribute to improve the modeling of processes in the low atmosphere.
287
RE02
THE REVISED METHANE DATABASE IN HITRAN 2012
15 min 9:05
LINDA R. BROWN, Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Dr.,
Pasadena, CA 91109.
The new compilation of methane molecular line parameters will be described.a Updates incorporate new global analyses
and measurements for 12 CH4 , 13 CH4 and 12 CH3 D. With a minimum intensity (in cm/molecule at 296 K) set to 10−37 for
the far-IR and 10−29 for the mid- and near-IR, the new database contains nearly 650,000 lines between 0 and 11502 cm−1 ,
more than double the 290,000 methane lines in HITRAN 2008. Part of the database size occurs because the minimum
intensity criterion for the new calculated infrared transitions is lowered by two orders of magnitude to include weaker
transitions important for outer planet and exoplanet atmospheres. Some 74000 lines from the 2008 HITRAN methane
database are retained: 13 CH4 from 6 to 8 µm, ν6 of 13 CH3 D near 8.7 µm, 12 CH3 D (7 - 4076 cm−1 ) and CH4 (4800
to 5550 cm−1 and 8000 to 9200 cm−1 ). New global analyses for 12 CH4 and 13 CH4 bands provide better predictions of
the dyad, pentad and octad vibrational states up through 2.2 µm. For the first time, 12 CH3 D and 13 CH4 bands near 2.3
µm are included. Above 5550 cm−1 , the new database consists of many more observed line positions and intensities.
Some 20,000 of the lines from prior laboratory results are replaced by over 68,000 features measured by new FTIR (5550
to 5852 cm−1 ) and DAS and CRDS (5852 to 7912 cm−1 ) studies reported since 2009. Intensities retrieved at cold and
room temperatures provide empirical lower state energies for many observed 12 CH4 , 13 CH4 and 12 CH3 D features; where
possible, confirmed quantum assignments are included. Finally, over 11000 measured positions, intensities and empirical
lower state energies from cold CH4 are compiled for the first time between 10923 and 11502 cm−1 . Available Voigt
pressure broadening measurements from HITRAN 2008 are transferred into the new compilation, but most lines are given
crudely-estimated coefficients. New measured intensities and nitrogen- and self-broadening coefficients are inserted for
selected far-IR transitions. In addition, high accuracy measured line positions are used for selected ν3 and 2ν3 transitions.
The substantial contributions from many different investigators will be shown.b
a This
compilation results from the work of many authors whose names will be cited in the oral presentation.
of the research described in this paper was performed at the Jet Propulsion Laboratory, California Institute of Technology, under contracts and
cooperative agreements with the National Aeronautics and Space Administration.
b Part
RE03
HITRAN2012 AND REMOTE SENSING OF PLANETARY ATMOSPHERES
15 min 9:22
For the recently-released HITRAN2012 edition a of the database, a substantial effort was taken to extend the HITRAN
database to have capabilities for studying a variety of planetary atmospheres. Spectroscopic parameters for gases and
spectral bands of molecules that are germane to the studies of planetary atmospheres have been assembled. These parameters include the types of data that have already been considered for transmission and radiance algorithms, such as
line position, intensity, broadening coefficients, lower-state energies, and temperature dependence values. Besides adding
new bands and isotopologues to the relevant molecules that already exist in HITRAN (methane, hydrogen halides, hydrogen disulfide, etc.), a number of new molecules, namely H2 , CS, C4 H2 , HC3 N and SO3 have been incorporated into the
HITRAN2012 database. For some of the molecules, additional parameters, beyond what is currently considered for the
terrestrial atmosphere, have been archived. Examples are pressure-broadened half widths due to various foreign partners.
Collision-induced absorption data for a large variety of the collision partners are provided in HITRAN for the first time.
Future efforts, including preparation of a new edition of the HITEMP database, will be discussed.
Note that another talk is given in the "Atmospheric Species" session, describing HITRAN improvements towards remote
sensing of terrestrial atmosphere. This effort is supported by the NASA Planetary Atmospheres program, under the grant
NNX10AB94G.
a L.
S. Rothman, I. E. Gordon, et al. "The HITRAN 2012 molecular spectroscopic database," JQSRT, submitted 2013.
288
RE04
COSMIC-RAY IONIZATION AND HAZES ON HOT JUPITERS
15 min 9:39
PAUL B RIMMER, CHRISTIANE HELLING, SUPA, School of Physics and Astronomy, University of St
Andrews, KY16 9SS; CATHERINE WALSH, Leiden Observatory, P.O. Box 9513, NL-2300 RA Leiden, The
Netherlands.
The chemical evolution of life begins in the diffuse interstellar medium and culminates in the atmosphere and on the surface
of a planet. The origin of life on earth took place when the sun’s magnetic winds more efficiently reduced the number
of ambient galactic cosmic ray (CR) particles of energy < 1 GeV. We consider the chemical effect of galactic cosmic
ray exclusion on a giant gas planet < 1 AU from its host star. Taking our previous work on CR ionization within the
atmospheres of free-floating planets as a starting point, we utilize an ion-neutral chemical network for atmospheres under
initial conditions and physical parameters for a giant gas planet. These initial conditions and parameters are determined
by the Drift-Phoenix model atmosphere code, which simultaneously treats radiative transfer and dust nucleation, settling
and growth. Two cases are explored: a terrestrial CR spectrum and the same spectrum with a cut-off at 1 GeV. In the
second case, we find a reduction in complex carbon species, e.g. C2 H2 and C2 H4 , in the upper atmosphere. This result has
implications for the haze observed on GJ 1214b.
RE05
SPECTROSCOPY FOR HOT SUPER-EARTH EXOPLANETS
15 min 9:56
P.F. BERNATH and M. DULICK, Department of Chemistry & Biochemistry, Old Dominion University, 4541
Hampton Boulevard, Norfolk, VA, 23529-0126, USA.
Spectroscopic observations of exoplanets are now possible by transit methods and direct emission. Spectroscopic requirements for exoplanet atmospheres will be reviewed based on existing measurements and model predictions for hot Jupiters
and super-Earths. Super-Earths are exoplanets with masses in the range of about 2 to 10 Earth masses (i.e., between the
size of Earth and Neptune). Many of them have very short orbital periods like hot Jupiters and are also hot because of
proximity to their parent star. For example, Kepler-10b has a mass of 4.54 times that of Earth, a density of 8.74 g cm−3
and a surface temperature of 1833 K. More than thirty super-Earths have been discovered and the most interesting objects
are rocky planets such as Kepler-10b and CoRoT-7b. Schaefer et al. have calculated the chemical equilibrium composition
of super-Earths with temperatures in the range 500-4000 K based on the vaporization of silicate rocks similar to those of
the Earth’s continental crust and bulk silicate Earth. In addition to H2 O, CO2 , CH4 , CO and H2 found in hot Jupiters,
additional species such as SO2 , O2 , HCl, HF, NaCl, KCl, KF, KOH and NaOH are expected to be present. Similar to our
previous work on hot ammoniaa and hot methaneb, emission spectra of hot SO2 will be presented. Continuing work on
NaCl and KCl emission spectra will also be covered.
a Hargreaves,
b Hargreaves,
R. J., Li, G., and Bernath, P. F. 2011, Hot NH3 Spectra for Astrophysical Applications, Astrophys. J. 735, 111.
R. J., et al. 2012, Hot Methane Line Lists for Exoplanet and Brown Dwarf Atmospheres, Astrophys. J. 757, 46.
Intermission
289
RE06
10 min 10:30
SPECTROSCOPIC STUDY OF CYANOACETYLENE CATION: SLOW PHOTO-ELECTRON SPECTROSCOPY AND
AB-INITIO INVESTIGATIONS
AHMED MAHJOUB, MARTIN SCHWELL, YVES BENILAN, NICOLAS FRAY and MARIE-CLAIRE
GAZEAU, LISA UMR CNRS 7583, Univ. Paris Est Creteil & Univ. Paris Diderot, Institut Pierre Simon
Laplace,61 Ave du General de Gaulle, 94010, Creteil, France; GUSTAVO A. GARCIA and FRANCOIS
GAIE-LEVERL, Synchrotron SOLEIL, L’Orme des Merisiers, St.Aubin, B.P. 48, 91192, Gif-sur-Yvette Cedex,
France; NORBERT CHAMPION and SYDNEY LEACH, LERMA UMR CNRS 8112, Observatoire de ParisMeudon, 5 place Jules-Jansen, 92195, Meudon, France.
Cyanoacetylene is one of the key minor constituents in the atmosphere of
Titan. The ion HCCCN+ has been detected in this atmosphere and it is
supposed to be formed by the reaction between C3H2+ and atomic nitrogena . We present here a spectroscopic investigation of the cyanoacetylene
cation using photoexcitation of the neutral by vacuum-ultraviolet (VUV)
synchrotron radiation coupled to a velocity map imaging electron/ion coincidence spectrometerb. The cation spectroscopy is studied by the Slow
Photoelectron Spectroscopy technique (SPES) (figure below) and the Total
Ion Yield (TIY). The TIY has been calibrated to absolute units using the known propane absolute cross-section. Quantum chemical calculations are performed in order to interpret these spectra. These calculations deal with the equilibrium
geometries, electronic-state patterns and evolutions, and harmonic and anharmonic wavenumbers. Through this study, we
observe, in the auto-ionization region above the ionization energy, a number of Rydberg series of neutral cyanoacetylene.
These Rydberg series converge to the first and second excited states of the cation.
Acknowledgments. We are indebted to the general technical staff of Synchrotron Soleil for the running facility.
a C.
b L.
Barrientos, P. Redondo and A. Largo J. Chem. Phys. A 104(49), 11541-11548. 2000
Nahon, N. De Oliveria,J. F. Gil,B. Pilette,O. Marcouillé, B. La garde and F. Polack Journal of Synchrotron Radiation 19(4), 508-520; 2012
RE07
15 min
THE ν12 + ν6 − ν6 AND ν11 − ν12 BANDS OF
THE FOUR LOWEST VIBRATIONAL STATES
12
CH13
3 CH3 :
10:42
A FREQUENCY ANALYSIS INCLUDING DATA FROM
N. MOAZZEN-AHMADI, J. NOROOZ OLIAEE, Department of Physics and Astronomy, University of Calgary, 2500 University Dr., N.W., Calgary, Alberta T2N 1N4, Canada; V.-M. HORNEMAN, Department of
Physical Sciences, University of Oulu, P.O. Box 3000, Fin-90014 Oulu, Finland.
High-resolution infrared spectra of the ν12 + ν6 − ν6 (around 820 cm−1 ) and ν11 − ν12 (around 370 cm−1 ) bands of
CH13
3 CH3 are assigned. Frequencies from these bands together with data from the ν12 and ν5 fundamentals and the torsional bands were analysed in a 4-state fit to determine the torsion mediated Coriolis and Fermi interactions. As compared
to normal ethane this lower symmetry isotopologue shows more complicated vibrational couplings. The combined data set
includes more than 6800 frequencies and was fitted to within experimental accuracy using a 77-parameter Hamiltonian.
The first determination of molecular parameters for the ν11 state of 12 CH13
3 CH3 has been made and using this Hamiltonian
we have provided lower state energies and partition functions between 100 and 330 K in increment of 10 K for planetary
data analysis.a A comparison with a 4-state fit of similar data for 12 CH12
3 CH3 will be made.
12
a N.
Moazzen-Ahmadi, J. Norooz Oliaee, and V.-M. Horneman, JQSRT, submitted.
290
RE08
15 min 10:59
IDENTIFICATION OF PROTONATED PYRENE (1-C16 H11+ ) AND ITS NEUTRAL COUNTERPART ISOLATED IN
SOLID PARA-HYDROGEN
MOHAMMED BAHOU, Department of Applied Chemistry and Institute of Molecular Science, National
Chiao Tung University, Hsinchu 30010, Taiwan; YU-JONG WU, National Synchrotron Radiation Research
Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan; YUAN-PERN LEE, Department
of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010,
Taiwan and Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan.
Protonated polycyclic aromatic hydrocarbons (H+ PAH) have been reported to have infrared (IR) bands at wavenumbers
near those of unidentified infrared (UIR) emission bands from interstellar objects. We report the IR spectra of protonated
pyrene (1-C16 H11 + ) and hydropyrenyl radical (1-C16 H11 ) trapped in solid para-hydrogen (p-H2 ). These species were
produced on electron bombardment of a mixture of p-H2 and pyrene during deposition. The IR features of 1-C16 H11 + were
identified on observing the decay of IR lines, whereas those of 1-C16 H11 were identified with increased intensity, after the
matrix sample was maintained in darkness for an extended period or upon irradiation of the matrix sample with UV light at
365 nm. Observed relative intensities and wavenumbers agree satisfactorily with the IR intensities and scaled vibrational
wavenumbers predicted for these species with the B3PW91/6-311++G(2d, 2p) method. Compared with literature spectra of
protonated polycyclic aromatic hydrocarbons recorded previously with IR photodissociation of Ar-tagged compoundsa or
IR multiphoton dissociation, b our method has the advantages of producing IR spectra with high resolution, true intensity
and wide spectral coverage for both protonated polycyclic aromatic hydrocarbons and their neutral counterparts. This
method is relatively clean with little interference from fragmentation and can be readily applied to larger H+ PAH.
a A.
b O.
M. Ricks, G. E. Douberly and M. A. Duncan, Astrophys. J. 702, 301 (2009).
Dopfer, PAHs and the Universe, 46, 103 (2011).
RE09
15 min 11:16
VIBRONIC SPECTROSCOPY OF A STRUCTURAL ISOMER OF QUINOLINE: (Z)-PHENYLVINYLNITRILE
DEEPALI N. MEHTA-HURT, JOSEPH A. KORN, and TIMOTHY S. ZWIER, Department of Chemistry,
Purdue University, West Lafayette, IN 47907-2084 U.S.A..
This talk will present results of a gas phase, jet-cooled vibronic spectroscopy study of (Z)-phenylvinylnitrile ((Z)-C6 H5 CH=CH-C=N, (Z)-PVN). With a substituent locked into a cis conformation with respect to the aromatic ring, (Z)-PVN
is postulated to be a molecule with an ideal functionality to isomerize to quinoline upon photoexcitation. As such, (Z)PVN is particularly relevant to Titan’s nitrile-containing atmosphere, where much of the chemistry is photochemically
driven. As a first step towards such photochemical studies, a fluorescence excitation spectrum of a mixture of (E)- and
(Z)-PVN was collected spanning the range 33,300-35,580 cm−1 (300.0-281.0 nm). Previous investigations in the Zwier
group pertaining to the vibronic spectroscopy of (E)-PVN allowed for the identification of peaks in the (E)- and (Z)-PVN
composite spectrum that were solely due to (Z)-PVN, and the S0 -S1 origin of (Z)-PVN was identified as a dominant band
that occurs at 33,706 cm−1 . For additional confirmation, ultraviolet depletion spectroscopy (UVD) was used to obtain an
isomer specific spectrum of (Z)-PVN as well as search for non-radiative transitions. Dispersed fluorescence spectra that
characterize the vibronic activity have also been acquired. A comparison between the vibronic spectroscopy of (Z)-PVN
with both (E)-PVN and (Z)-phenylvinylacetylene ((Z)-PVA), the hydrocarbon analog of (Z)-PVN, will be made in this
talk.
291
RE10
15 min 11:33
HIGH RESOLUTION INFRARED SPECTRA OF PLASMA JET-COOLED DI- AND TRIACETYLENE IN THE C-H
STRETCH REGION BY CW CAVITY RING-DOWN SPECTROSCOPY
D. ZHAO, J. GUSS, A. WALSH, K. DONEY, H. LINNARTZ, Sackler Laboratory for Astrophysics, Leiden
Observatory, University of Leiden, P.O. Box 9513, NL-2300 RA Leiden, the Netherlands.
Polyacetylenes form an important series of unsaturated hydrocarbons that are of astrophysical interest. Small polyacetylenes have been detected from infrared observations in dense atmosphere of Titan and in a protoplanetary nebula
CRL 618. We present here high-resolution mid-infrared spectra of diacetylene (HC4 H) and triacetylene (HC6 H) that are
recorded in a supersonically expanded pulsed planar plasma using an ultra-sensitive detection technique. This method
uses an all fiber-laser-based optical parametric oscillator (OPO), in combination with continuous wave cavity ring-down
spectroscopy (cw-CRDS) as a direct absorption detection toola . A hardware-based multi-trigger concept is developed to
apply cw-CRDS to pulsed plasmas.
Vibrationally hot but rotationally cold HC4 H and HC6 H are produced by discharging a C2 H2 /He/Ar gas mixture which
is supersonically expanded into a vacuum chamber through a slit discharge nozzle. Experimental spectra are recorded at
a resolution of ∼100 MHz in the 3305-3340 cm−1 region, which is characteristic of the C-H stretch vibrations of HC4 H
and HC6 H. Jet-cooling in our experiment reduces the rotational temperature of both HC4 H and HC6 H to <20 K. In total,
∼2000 lines are measured. More than fourteen (vibrationally hot) bands for HC4 H and four bands for HC6 H are assigned
based on Loomis-Wood diagrams, and nearly half of these bands are analyzed for the first time. For both molecules
improved and new molecular constants of a series of vibrational levels are presented. The accurate molecular data reported
here, particularly those for low-lying (bending) vibrational levels may be used to interpret the ro-vibrational transitions in
the FIR and submillimeter/THz region.
a D.
Zhao, J. Guss, A. Walsh, H. Linnartz Chem. Phys. Lett., dx.doi.org/10.1016/j.cplett.2013.02.025, in press, 2013.
292
RF. ASTRONOMICAL SPECIES AND PROCESSES
Chair: NICK INDRIOLO, Johns Hopkins University, Baltimore, MD
RF01
15 min 1:30
DISTRIBUTION OF SO2 AND SO IN THE ENVELOPE OF VY-CANIS MAJORIS: INSIGHT INTO CIRCUMSTELLAR SULFUR CHEMISTRY
Tucson, 85721; ,.
Millimeter wave observations of SO2 and SO in the envelope of the O-rich supergiant VY-Canis Majoris have been conducted with the Submillimeter Telescope (SMT) of the Arizona Radio Observatory, between 210 and 290 GHz. A non LTE
radiative transfer code has been written to fit the line profile of 22 lines of SO2 and 5 transitions of SO, and model their
abundance and distribution within the circumstellar envelope. The rotational levels involved span a wide energy range,
from 13 cm−1 to 104 cm−1 for SO2 , and 17 to 40 cm−1 for SO. The high number of transitions fitted provides strong constraints on the excitation conditions, hydrogen density and kinetic temperatures. The results will be discussed in relation
to the formation processes and chemistry of these two species in O-rich molecular envelopes.
RF02
RADIO INTERFEROMETRIC DETECTION OF TiO AND TiO2 IN VY CANIS MAJORIS:
"SEEDS" OF INORGANIC DUST FORMATION
15 min 1:47
S. BRÜNKEN, H.S.P. MÜLLER, I. Physikalisches Institut, Universität zu Köln, 50937 Köln, Germany ; T.
KAMIŃSKI, K.M. MENTEN, Max-Planck Institut für Radioastronomie, 53121 Bonn, Germany; C.A. GOTTLIEB, N.A. PATEL, K.H. YOUNG, M.C. McCARTHY, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA 02138, USA; J.M. WINTERS, Institut de Radioastronomie Millimétrique, 38406 Saint-Martin
d’Héres, France; L. DECIN, Instituut voor Sterrenkunde, Katholieke Universiteit Leuven, 3001 Leuven, Belgium, and Sterrenkundig Instituut Anton Pannekoek, University of Amsterdam, 1098 Amsterdam, The Netherlands.
Circumstellar envelopes around late-type stars harbour a rich variety of molecular gas and copious amounts of dust, originating from the mass-loss of the central star during the asymptotic giant branch (AGB) or the red supergiant phase. The
formation of dust in these objects, in particular the first nucleation stages out of gas phase molecules, is still poorly understood. Here we report the first detection of pure rotational transitions of the two simplest titanium oxides, TiO and TiO2 ,
towards the oxygen-rich red supergiant VY Canis Majoris (VY CMa). This actually represents the first secure identification of TiO2 in space. Observations of several rotational emission lines of both species with the Submillimeter Array
(SMA) in the 345 GHz-band and with the IRAM Plateau de Bure Interferometer (PdBI) around 220 GHz confirm the
presence of these refractory species in the cool (<1000 K) circumstellar envelope in a region several times the size of the
dust formation zone. The role of Ti oxides as "seeds" of inorganic dust formation in oxygen-rich circumstellar envelopes
will be discussed in view of the present observations.
293
RF03
TRANSITION-METAL OXIDES IN WARM CIRCUMSTELLAR ENVIRONMENTS
15 min 2:04
MIROSŁAW R. SCHMIDT , N. Copernicus Astronomical Center, Department of Astrophysics, PL-87-100
Toruń, ul. Rabiańska 8, Poland ; TOMASZ KAMIŃSKI , Max Planck Institut für Radioastronomie, Auf
dem Hügel 69, 53121 Bonn, Germany ; and ROMUALD TYLENDA , N. Copernicus Astronomical Center,
Department of Astrophysics, PL-87-100 Toruń, ul. Rabiańska 8, Poland.
We report on detections and simulations of electronic bands of transition-metal oxides, i.e. ScO, TiO, VO, CrO, YO,
and of AlO, in spectra of two red novae V838 Mon and V4332 Sgr. These objects experienced a stellar merger event in
2002 and 1994, respectively, and have very rich circumstellar environments abundant in dust and molecules. We analyzed
optical spectra of V838 Mona which show a presence of outflowing material. In this object, electronic systems of oxides
are observed in absorption against a photospheric spectrum which resembles that of a late-type supergiant. We present
simulations of the absorption bands which allowed us to derive the excitation temperatures of 300–500 K and constrain
column densities, which turned out to be very high. Among many interesting features discovered, we identified forbidden
transitions of TiO in the b1 Π-X3 ∆ and c1 Φ-X3 ∆ systems, which are seen owing to the high column densities and the
relatively low temperatures. In the case of the older red nova V4332 Sgrb , the main object is surrounded by a circumstellar
disc which is seen almost edge-on and obscures the central star. The molecular spectra are seen in emission in this object,
what is very unusual in astrophysical sources observed at optical wavelengths. We show that these emission bands arise
owing to the special geometry of the star-disk system and that radiative pumping is responsible for excitation of the
molecules. From the shapes of the rotational contours, we derive temperatures of about 120 K in this object. Remarkably,
the spectra of V4332 Sgr contain features of CrO, which is the first identified signature of this molecule in an astrophysical
object. In addition to the excitation and radiative-transfer analysis of the molecular spectra, we discuss chemical pathways
that could lead to the observed variety of metal oxides seen in these enigmatic sources.
a T.
b T.
Kaminski, M. Schmidt, R. Tylenda, M. Konacki, and M. Gromadzki ApJSuppl., 182 (33), 2009.
Kaminski, M. Schmidt and R. Tylenda Astronomy and Astrophysics, 522 (A75), 2010.
RF04
15 min 2:21
OBSERVATIONS AND ANALYSIS OF EXTENDED TAIL TOWARD RED IN THE DIFFUSE INTERSTELLAR
BANDS OF HERSCHEL 36
TAKESHI OKA, Department of Astronomy and Astrophysics, University of Chicago, Chicago, IL 60637;
DANIEL E. WELTY, SEAN JOHNSON, DONALD G.YORK, LEW M. HOBBS, Department of Physics and
Astronomy, Carthage College, Kenosha, WI 53140; and JULIE DAHLSTROM,.
In the studies of the Diffuse Interstellar Bands (DIBs), the sightline toward Herschel 36 near the center of the HII region
Messier 8 is unique. It shows spectra of CH+ and CH in the first excited level indicating the presence of a cloud with high
radiative temperature. The heating is most likely due to far infrared emission from the adjacent intense infrared source Her
36 SE at a distance of 0.25" from Her 36.a
The effect of the high radiative temperature on some DIBs is spectacular. It produces on a normally symmetric bell-shape
line a very prominent Extended Tail toward Red (ETR) on prototypical DIBs λ 5780.5, λ 5797.1, and λ 6613 while other
DIBs λ 5849.8, λ 6196.0, and λ 6379.3 are little affected. We interpret this as indicating that the carriers of the former 3
DIBs that are seriously affected by the radiation are polar molecules and the pronounced ETRs are the result of the decrease
of rotational constant B (3 - 5 %) upon electronic excitation. High J rotational levels are pumped radiatively and with the
negative (B’ - B) produces the ETR.
We have developed a model calculation of rotational distribution taking into account of both radiative and collisional
processes. In view of the complexity of the problem linear molecules are considered. 7 parameters enter into the calculation
but we find the fractional variation of B and the radiative temperature Tr are the most decisive. Although molecules with
a general shape is beyond the scope of this work, we conclude that the 3 DIBs which show the pronounced ETRs are
due to polar molecules and the requirement of high variation of B indicates that the molecules are not that large perhaps
composed of 3-6 heavy atoms. The 3 DIBs that do not show the pronounced ETRs are likely due to non-polar molecules
or large polar molecules with small fractional variation of B.b
a Goto,
b Oka,
M., Stecklum, B., Linz, H., Feldt, M., Henning, Th., Pascucci, I., and Usuda, T. 2006, ApJ, 649 299.
T., Welty, D. E., Johnson, S., York, D. G., Dahlstrom, J., and Hobbs, L. M. 2013, ApJ, submitted
294
RF05
15 min 2:38
MULTI-RESOLUTION STUDIES OF COMPLEX MOLECULES IN HIGH MASS STAR FORMING REGIONS
DOUGLAS N. FRIEDEL, Department of Astronomy, University of Illinois, 1002 W. Green St., Urbana, IL
61801.
After our successful molecular studies of the high mass star forming region Orion-KL (Friedel & Widicus Weaver 2012,
ApJS, 201, 17; Widicus Weaver & Friedel 2012, ApJS, 201, 16) we have observed three more high mass star forming
regions (W3, W75N, and W51). The purpose of these observations is to further constrain the physical conditions under
which the different complex organic molecules form and survive. The results of these observations as well as their impact
on current molecular formation models will be presented.
RF06
15 min 2:55
IONIZATION OF H2 BY X-RAYS IN THE CENTRAL MOLECULAR ZONE OF THE GALACTIC CENTER
MASAHIRO NOTANI and TAKESHI OKA, Department of Astronomy and Astrophysics and Department of
Chemistry, the Enrico Fermi Institute, the University of Chicago, Chicago, Illinois, 60637, USA.
Recent studies of the Galactic center using the infrared spectrum of H+
3 have revealed a high ionization rate of H2 on the
order of ζ ∼ 3×10−15 s−1 in wide regions of the Central Molecular Zone (CMZ), a region with a radius of ∼ 150 pc at the
Galactic center.ab So far we have ascribed this ionization rate, which is an order of magnitude higher than in the Galactic
disk, to cosmic rays because of a high density of supernova remnants in the CMZ. In view of the abundant intense X-ray
sources from 1 keV to several 10 keV in the region, however, there may be a significant ionization by X-rays also.
We estimate the ionization rate due to X-rays based on the large scale ART-P X-ray map of the Galactic center region.c
The calculations proceed in two steps. First we allow for the attenuation of the observed X-rays by the foreground gas to
obtain the original intensities of the X-ray sources.d We then use the corrected X-ray flux to calculate ionization rates of
H2 in the CMZ. The calculation is also related to the heating of the gas by X-rays. Discussion of the details of calculations
and the results will be presented.
a Oka,
T., Geballe, T. R., Goto, M., Usuda, T., and McCall, B. J. 2005, ApJ, 632 882
T. R., and Oka, T. 2010, ApJ, 709 L70.
c Pavlinskii, M. N., Grebenev, S. A., and Syunyaev, R. A. 1992, Sov. Astron. Lett., 18 116.
d Morrison, R. and McCammon, D. 1983, ApJ, 270 119.
b Geballe,
RF07
CARMA OBSERVATIONS OF PAH RICH SOURCES: NGC 2023, L134N AND GGD 27
15 min 3:12
P. BRANDON CARROLL, BRETT A. MCGUIRE, Department of Chemistry, California Institute of Technology, Pasadena CA, 91125; GEOFFREY A. BLAKE, Divisions of Geological and Planetary Sciences and
Chemistry and Chemical Engineering, California Institute of Technology, Pasadena CA, 91125.
Polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic nitrogen heterocycles (PANHs) have been the focus of
intense astrochemical interest in recent years. PA(N)Hs account for up to 20% of the interstellar carbon budget and are
believed to play key roles in many chemical and physical processes in the ISM. Evaluation of the extent to which PA(N)Hs
influence these processes is hampered by our inability to detect PA(N)Hs concurrently with other chemical species using
radio astronomy, due to their low dipole moments and large partition functions. An alternative is to observe regions with
previous infrared detection and mapping of PA(N)Hs and correlate radio and infrared observations. We have conducted 3
mm CARMA C and D configuration observations of three PA(N)H rich sources that have been previously observed in the
infrared: NGC 2023, L134N, and GGD 27. We will report the results of our analysis in the context of PA(N)H observations.
295
RF08
15 min 3:29
A SEARCH FOR HCO AND HCN EMISSION IN PLANETARY NEBULAE
+
DEBORAH R. SCHMIDT, Department of Astronomy, Steward Observatory, The University of Arizona, Tucson, AZ 85721; and LUCY M. ZIURYS, Department of Chemistry and Biochemistry, Department of Astronomy, Steward Observatory, The University of Arizona, Tucson, AZ 85721.
It was initially believed that molecular material from the AGB (asymptotic giant branch) phase of a 1-8 solar mass star’s
evolution would be photodissociated by intense ultraviolet radiation from the star as it evolves during the subsequent
planetary nebula stage. However, detections of CO and H2 in numerous planetary nebulae (PNe) have shown that the
chemistry of these objects is more complicated than previously anticipated. A fuller understanding of the molecular
abundances of PNe is vital to our understanding of their environments; thus, it is necessary to build up the sample of PNe
which have had their molecular content studied in depth. We are conducting a search for HCO+ and HCN in seventeen
planetary nebulae that have previously been detected in CO, as both molecules are expected to be readily detectable if
present and could be used to locate the highest density material in PNe. Observations of the J = 1 → 0 transitions of HCO+
and HCN (at 89 GHz and 88 GHz respectively) are being conducted using the 12-Meter Telescope of the Arizona Radio
Observatory (ARO), while measurements of the J = 3 → 2 transitions (at 265 GHz for HCN and 267 GHz for HCO+ )
are being made with the ARO Sub-Millimeter Telescope (SMT). The most current results of this search will be presented,
including radiative transfer analysis of the spectra to establish physical conditions and molecular abundances.
Intermission
RF09
15 min 4:00
IDENTIFICATION AND ASSIGNMENT OF THE FIRST EXCITED TORSIONAL STATE OF CH2 DOH WITHIN THE
o2 , e2 , AND o3 TORSIONAL LEVELS
Oak Grove Dr., Pasadena, CA 91109, USA; L. H. COUDERT, LISA, CNRS/Universités Paris Est et Paris
Diderot, 61 Avenue du Général de Gaulle, 94010 Créteil, France; L. MARGULÈS, R. A. MOTIYENKO,
Theoretical models describing the details of asymmetric-top asymmetric-frame internal rotation remain to be fully developed and tested especially in excited torsional states. The spectrum of CH2 DOH offers a unique opportunity to test and
develop asymmetric-top asymmetric-frame internal rotation theory. The theoretical energy levels predicted by El Hilali et
al.a and combination differences of the 76 assigned torsional subbands coupled with the experimental microwave energy
levels of the ground stateb served as a basis for assigning the excited torsional state. The existing microwave spectra was
supplemented with recordings of 1308–2010 GHz and 2450–2700 GHz. This facilitated extension of the ground state
assignments to K = 14 and identified a number of torsional interactions. In this paper we report assignment of the o2 ,
e2 , and o3 torsional levels to K = 9. All the torsional levels in the first excited torsional state have been connected with
microwave accuracy transitions except o3 K = 2. Strong rotational interactions between the o2 K = 0 and K = 2 states
and the e2 K = 4, o2 K = 1, o3 K = 2 and o3 K = 3 levels are observed. A week avoided crossing between e1 K = 12
and e2 K = 8 at J = 20 has also been identified. When the microwave results are combined with the existing infrared
assignments it is now possible to predict the entire vt = 0 to vt = 1 torsional band to better than infrared experimental
accuracy, greatly simplifying subsequent infrared assignments.
a El
Hilali, Coudert, Konov, and Klee, J. Chem. Phys. 135 (2011) 194309.
Yu, and Drouin, J. Mol. Spectrosc. 280 (2012) 119.
b Pearson,
296
RF10
15 min 4:17
ANALYSIS OF THE ROTATION-TORSION SPECTRUM OF CH2 DOH WITHIN THE e0 , e1 , AND o1 TORSIONAL
LEVELS
Créteil, France; JOHN C. PEARSON, SHANSHAN YU, Jet Propulsion Laboratory, California Institute
of Technology, 4800 Oak Grove Dr., Pasadena, CA 91109, USA; L. MARGULÈS, R. A. MOTIYENKO,
Since the first assignments of Quade and coworkers,a a more satisfactory understanding of the spectrum of CH2 DOH has
now been achieved. Thanks to a multidimensional potential energy surfaceb and to a new theoretical approach accounting
for the internal rotation of a partially deuterated methyl group,c 76 torsional subbands could be identified in the microwave
and FIR domains. 8356 rotation and rotation-torsion transitions were also assigned for the three lowest lying torsional
levels, e0 , e1 , and o1 , in the microwave and terahertz domainsd and were analyzed with empirical models.
In this paper, a new approach aimed at accounting for the rotation-torsion energy levels of CH2 DOH will be presented. It
is based on the exact expression of the generalized 4 × 4 inertia tensor of the moleculee and accounts for the Cs symmetry
of the partially deuterated methyl group, for the dependence of the rotational constants on the angle of internal rotation,
and for the rotation-torsion Coriolis coupling. This approach will be used to analyze high-resolution data involving the
three lowest lying torsional levels, up to k = 11. In addition to the microwave data reported recently,d new transitions
recorded in the terahertz domain at JPL will be analyzed. The results of the analysis will be presented in the paper and the
parameters determined in the analysis will be discussed.
a Quade
and Suenram, J. Chem. Phys. 73 (1980) 1127; and Su and Quade, J. Mol. Spec. 134 (1989) 290.
Coudert, Klee, and Smirnov, J. Mol. Spec. 256 (2009) 204.
c El Hilali, Coudert, Konov, and Klee, J. Chem. Phys. 135 (2011) 194309.
d Pearson, Yu, and Drouin, J. Mol. Spec. 280 (2012) 119.
e Quade and Lin, J. Chem. Phys. 38 (1963) 540.
b Lauvergnat,
RF11
15 min 4:34
A GLOBAL FIT OF THE X Π, A Σ , B Σ AND C Σ STATES OF SIX OH ISOTOPOLOGUES
2
2
+
2
+
2
+
SHANSHAN YU, JOHN C. PEARSON AND BRIAN J. DROUIN, Jet Propulsion Laboratory, California
Institute of Technology, Pasadena, CA 91109.
We report the preliminary results on a global fit of six OH isotopologues, 16 OH, 17 OH, 18 OH, 16 OD, 17 OD and 18 OD,
with the purpose to support the current and future astrophysical and atmospheric remote sensing missions. The primary
goal of our project is to simultaneously fit the MW, THz, infrared, visible, and UV data of the six OH isotopologues using
a global Dunham model and to predict all known and as yet unmeasured transitions for any of the six isotopologues within
state-of-the-art experimental uncertainty. Within the framework of a Dunham fit, all isotopologues can be treated as the
same molecule using well-known reduced mass relationships (see our similar work on O2 in Yu et al.a ). Experimental
information from one isotopologue can be leveraged to accurately predict the spectra of any other isotopologue. All previously available experimental data from the following systems were collected and used in the analysis: the microwave
transitions in the X 2 Π state, the mid- and near-infrared vibration-rotation transitions in the X 2 Π state, and the UV electronic transitions from the A2 Σ+ − X 2 Π, B 2 Σ+ − X 2 Π, B 2 Σ+ − A2 Σ+ , C 2 Σ+ − A2 Σ+ systems. For the main 16 OH
isotopologue, experimental data are available for the following vibrational states: v = 0 − 13 for X 2 Π, v = 0 − 2, 4 − 9
for A2 Σ+ , v = 0 − 1 for B 2 Σ+ , v = 0 − 1 for C 2 Σ+ . Band by band fits are first carried out for these 16 OH data to
discover problematic measurements, e.g., misassigments and calibration problems. Then all these 16 OH data were fitted
with a Dunham-type model. Band by band fits are in progress for each of the other five minor isotopologues. Eventually
data from all the six isotopologues will be simultaneously fitted with an isotopically invariant Dunham-type model. We
will present the most recent fitting results.
a S. Yu, C. E. Miller, B. J. Drouin and H.S.P. Müller, igh resolution spectral analysis of oxygen I. isotopically invariant Dunham fit for the X 3 Σ− ,
g
a1 ∆g , and b1 Σ+
g states J. Chem. Phys. 137 (2012) 024304.
297
RF12
MICROWAVE SPECTROSCOPY OF TRANS-ETHYL METHYL ETHER IN THE GROUND STATE
15 min 4:51
KAORI KOBAYASHI, YUSUKE SAKAI, SHOZO TSUNEKAWA, Department of Physics, University of
Toyama, 3190 Gofuku, Toyama, 930-8555 Japan; TAIHEI MIYAMOTO, MASAHARU FUJITAKE and
NOBUKIMI OHASHI, Kanazawa University, Japan.
The trans-ethyl methyl ether molecule (CH3 CH2 OCH3 ) has two inequivalent methyl group internal rotors which corresponds to the two vibrational motions, ν28 and ν29 . Due to these internal rotations, a rotational transition could be split
into maximum five components. The skeletal torsion (ν30 ) is another low-lying state (ν30 ) that interacts with the ν28 and
ν29 modes. The microwave spectra of the trans-ethyl methyl ether molecule in the ν28 = 1 a , ν29 = 1b , and ν30 = 1c , 2
and 3d have been extensively studied by using Hougen’s tunneling matrix formalism. The microwave spectroscopy in the
ground state was studied by several groups e, f, g, h . The splitting due to the ν28 mode (C-CH3 internal rotation) is small in
the ground state and was not fully resolved in most of the previous studied rotational transitions.
In this paper, we report the results of the pulsed nozzle-jet Fourier transform microwave spectroscopy so as to measure the
fully resolved spectra. The submillmeter wave spectroscopy was also carried out. Our analysis including the previously
reported transitions would be useful for astronomical observations.
a K.
Kobayashi, T. Matsui, N. Mori, S. Tsunekawa, and N. Ohashi J. Mol. Spectrosc. 269, 242 2011.
Kobayashi, T. Matsui, S. Tsunekawa, and N. Ohashi J. Mol. Spectrosc. 255, 164 2009.
c K. Kobayashi, T. Matsui, N. Mori, S. Tsunekawa, and N. Ohashi J. Mol. Spectrosc.251, 301 2008.
d K. Kobayashi, K. Murata, S. Tsunekawa, and N. Ohashi Int. Symposium on Mol. Spectrosc., 65th Meeting TH15 2010.
e M. Hayashi, and K. Kuwada J. Mol. Structure 28, 147 1975.
f M. Hayashi, and M. Adachi J. Mol. Structure 78, 53 1982.
g S. Tsunekawa, Y. Kinai, Y. Kondo, H. Odashima, and K. Takagi Molecules 8, 103 2003.
h U. Fuchs, G. Winnewisser, P. Groner, F. C. De Lucia, and E. Herbst Astrophys. J. Suppl. 144, 277 2003.
b K.
RF13
JET-COOLED EXCITATION SPECTRA OF LARGE BENZANNULATED
ANTHRACENYLMETHYL (C15 H11 ) and 1-PYRENYLMETHYL (C17 H11 )
BENZYL
15 min 5:08
RADICALS: 9-
GERARD D. O’CONNOR, GEORGE B. BACSKAY, GABRIELLE V.G. WOODHOUSE, TYLER P. TROY,
KLAAS NAUTA, SCOTT H. KABLE and TIMOTHY W. SCHMIDT, School of Chemistry, The University of
Sydney, NSW 2006, Australia.
The jet-cooled D1 ← D0 excitation spectra of two benzannulated benzyl radicals (BBRs), 9-anthracenylmethyl (9-AnMe)
and 1-pyrenylmethyl (9-PyMe), have been obtained using mass-resolved resonant two-colour two-photon ionization spectroscopy (R2C2PI). Analysis of the spectra in view of symmetry and calculated vibrational frequencies indicate significant
vibronic coupling. From the spectrum of 9-AnMe we elucidate significant anharmonicity in the excited state. This anharmonic behaviour is examined computationally through both TDDFT and ab initio methods. Excited state properties
of 9-AnMe and 1-PyMe are examined with reference to the existing spectra of smaller BBRs. Trends in the observed
spectra of BBRs allow spectroscopic properties of larger BBRs to be predicted. These predictions suggest the D1 ← D0
transitions of large BBRs are unlikely to be carriers of the diffuse interstellar bands.
298
RF14
ROTATIONAL STRUCTURE OF THE IR/FIR BANDS OF SMALL PAHS
15 min 5:25
O. PIRALIa , S. GRUETa , M. VERVLOET, Ligne AILES, Synchrotron SOLEIL, L’Orme des Merisiers SaintAubin, 91192 Gif sur Yvette Cedex - France; M. GOUBET, T. R. HUET, Laboratoire de Physique des Lasers,
Atomes et Molécules, UMR 8523 CNRS - Université Lille 1, Bâtiment P5, F-59655 Villeneuve d’Ascq Cedex,
France; R. GEORGES, Université de Rennes 1, Institut de Physique de Rennes, CNRS, UMR 6251, F-35042
Rennes Cedex, France; P. SOULARD, P. ASSELIN, UPMC Université Paris 06, UMR 7075 CNRS, Laboratoire de Dynamique, Interactions et Réactivité (LADIR), F-75005, Paris, France.
Accurate spectroscopic measurements in the laboratory of PAH molecules are required to better understand their excitation/relaxation processes which could be responsible for the Unidentified Infrared Bands observed in various objects in
space. In particular very few is known concerning the rotational structure of the IR/FIR bands of PAHs. We used the
high resolution Fourier Transform interferometer of the AILES beamline of synchrotron SOLEIL to record the rotationally
resolved spectra of several IR/FIR vibrational modes of naphthalene (C10 H8 ) and its derivatives: quinoline (C9 H7 N), isoquinoline (C9 H7 N), azulene (C10 H8 ), quinoxaline (C8 H6 N2 ), quinazoline (C8 H6 N2 ). Firstly, the intense band associated
with the ν46 CH bending out of plane mode of naphthalene recorded under jet conditions (Jet-AILES experiment developed
on the AILES beamline by the IPR-LADIR-PhLAM consortium) revealed transitions involving low J and Ka rotational
quantum numbers. These new data permitted to accurately fit the ground state rotational constants and to improve the
ν46 band constantsb . As a second step, we performed the rotational analysis of the low frequency ν47 and ν48 bands of
naphthalene recorded at room-temperature in the long absorption pathlength cell from ISMO. As a last step, the high resolution spectra of several bands of azulene, quinoline, isoquinoline and quinoxaline were recorded at room temperature and
analyzed using the same procedure. All the rotational constants fitted in the present work were compared to the results of
anharmonic DFT calculations realized at various levels of accuracy.
a Also
b S.
Albert, et al.; Faraday Discussions, 150, 51 (2011)
RF15
15 min 5:42
SYNCHROTRON-BASED HIGHEST RESOLUTION FTIR SPECTROSCOPY OF AZULENE, NAPHTHALENE
(C10 H8 ), INDOLE (C8 H6 N) AND BIPHENYL (C12 H10 )
S. ALBERT, M. QUACK, PHYSICAL CHEMISTRY, ETH ZÜRICH, CH-8093 ZÜRICH, SWITZERLAND;
PH. LERCH, SWISS LIGHT SOURCE, PAUL-SCHERRER-INSTITUTE, CH-5232 VILLIGEN, SWITZERLAND.
Great progress has been made in resolution (∆ν ≤ 20 MHz) and sensitivity in the field of high resolution Fourier transform
infrared (FTIR) spectroscopy over the last decadea,b,c . In particular, the use of synchrotron sources such as the Swiss
Light Source (SLS)d have overcome one of the disadvantages of high resolution FTIR spectroscopy, the problem of noise
related to modest signal strength with broad band coverage from weak light sources. FTIR spectroscopy with synchrotron
sources now makes it possible to investigate scientific questions of fundamental physics and astrophysics. One of the great
challenges of astronomical infrared spectroscopy is the identification of the Unidentified Infrared Bands (UIBs) found in
several interstellar objects. Polycyclic Aromatic Hydrocarbons (PAHs) have been proposed to be the carrier of the UIBse .
For that reason we have started to investigate with our ETH-SLS interferometer the rotationally resolved FTIR spectra of
the bicyclic molecules naphthalene (C10 H8 )d and azulene (C10 H8 ) as a simple prototypical spectrum for a PAH infrared
spectrum and of indole (C8 H6 N) as a prototype of a bicyclic heteroaromatic system. We have analysed in high resolution
the ν46 band of naphthalene, the ν35 and 2ν40 bands of indole as well as the ν44 band of azulene. We have found a
coincidence between the ν46 fundamental of naphthalene and the UIB at 12.78 µm. A comparison of the biphenyl FTIR
spectrum with the UIBs in the range 13 to 15 µm illustrates a coincidence between the UIBs at 13.6 µm and 14.2 µm with
the major biphenyl bands.
a S.
Albert, K. Keppler Albert and M. Quack, Trend in Optics and Photonics 2003, 84, 177-180.
Albert and M. Quack, ChemPhysChem, 2007, 8, 1271-1281.
c S. Albert, K. Keppler Albert and M. Quack, High Resolution Fourier Transform Infrared Spectroscopy in Handbook of High Resolution Spectroscopy,
Vol. 2 (Eds. M. Quack and F. Merkt), Wiley, Chicester 2011, 965-1021.
d S. Albert, K.K. Albert, Ph. Lerch and M. Quack, Faraday Discussions 2011, 150, 71-99.
e A.G.G.M. Tielens, Annu. Rev. Astron. Astrophys. 2008, 46, 289.
b S.
299
RF16
15 min 5:59
PHOTOGENERATION OF, AND EFFICIENT COLLISIONAL ENERGY TRANSFER FROM, VIBRATIONALLY EXCITED HYDROGEN ISOCYANIDE (HNC)
MICHAEL J. WILHELMa , Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104;
and HAI-LUNG DAI, Department of Chemistry, Temple University, Philadelphia, PA 19122.
Time-resolved IR emission spectroscopy has previously been used to characterize the 193 nm photodissociation dynamics
of vinyl cyanide, H2 CC(H)CNb . Of significance, it was observed that the major molecular elimination channels generated
ro-vibrationally excited photofragments consisting of: HCN + H2 CC: and HNC + HCCH, for which the HCN / HNC
branching ratio was deduced to be 3.3 to 1. In the present study, we examine the collisional deactivation of the vibrationally excited (Evib =15 kcal mole−1 above the zero-point energy) ν1 NH and ν3 NC stretches of HNC, in response to
collisions with a series of inert rare-gas atoms: Rg=He, Ar, Kr, and Xe. Spectral modeling of the IR emission allows direct
determination of the time-dependent average internal energy of HNC, and therefore a quantification of the average energy
lost per collision, as a function of the internal energy. Similar to vibrationally excited radicalsc , collisional deactivation of
HNC is shown to be remarkably efficient, likely due to comparatively strong HNC / Rg intermolecular attractive interactions. Subsequently, depending upon the relative rates, excited HNC can either isomerize to the energetically more stable
HCN, or be rapidly quenched and kinetically trapped as HNC. Potential implications for the astrophysical HNC / HCN
abundance ratio problem will be discussed.
a Present
Address: Department of Chemistry, Temple University, Philadelphia, PA 19122
J. Wilhelm, M. Nikow, L. Letendre, and H. L. Dai J. Chem. Phys. 130, 044307 (2009).
c M. J. Wilhelm, M. Nikow, J. M. Smith, and H. L. Dai J. Phys. Chem. Lett. 4, 23 (2013).
b M.
300
RG. THEORY
Chair: SO HIRATA, University of Illinois, Urbana, IL
RG01
15 min 1:30
SYMMETRY, DEGENERACY, AND STATISTICAL WEIGHTS OF
H+
3
KYLE N. CRABTREE, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, 02138; BENJAMIN
J. McCALL, Departments of Chemistry, Astronomy, and Physics, University of Illinois, Urbana, IL, 61801.
High resolution spectroscopy of H+
3 is used to probe a variety of physical phenomena, from temperatures, densities,
and ionization rates of interstellar clouds to the fundamental chemical physics of chemical reactions involving identical
particles. Throughout the literature surrounding these applications, various assumptions, often implicit and sometimes
contradictory, are made concerning the degeneracies and statistical weights of the ortho and para nuclear spin modifications
of H+
3 , and it is often difficult to account for their origins and applicability. In this talk, the symmetry properties of the
nuclear spin and rovibrational wavefunctions of H+
3 are discussed in detail, as well as the selection rules that determine their
combinations. The findings from this close examination are presented in the context of the applications of H+
3 spectroscopy,
with the aim of explicitly identifying the degeneracies of individual rovibrational states. Finally, it is suggested that the
nuclear spin wavefunctions of para-H+
3 directly reveal branching fractions for the nuclear spin modifications of H2 formed
+
in proton transfer reactions of the form p-H+
3 + X → H2 + HX .
RG02
INVESTIGATION OF LARGE-AMPLITUDE MOTIONS OF
FER BETWEEN H+
3 and H2
15 min 1:47
H+
5
AND THE DYNAMICS OF THE PROTON TRANS-
ZHOU LIN and ANNE B. McCOY, Department of Chemistry and Biochemistry, The Ohio State University,
Columbus, OH 43210.
+
Protonated hydrogen dimer, or H+
5 , is the intermediate of the proton-transfer reaction between H3 and H2 . The dynamics of
this reaction has been postulated to play a significant role in the non-thermal H/D and ortho-/para- ratio in the interstellar
clouds. As a weakly-bound, fluxional molecular ion, H+
5 has a very rich vibrational spectrum. The large-amplitude
vibrational motions of H+
make
theoretical
studies
interesting
but challenging. This work aims at understanding how these
5
large-amplitude motions are reflected in the dynamics of the proton transfer between H+
3 and H2 , or between the deuterated
analogues of these two species. The shared-proton stretch mode is closely related to the proton-transfer process and is thus
of particular interest. Diffusion Monte Carlo calculations of minimum energy pathsa are performed for the ground state
and selected excited states, in order to explore how the vibrational energetics and wavefunctions evolve as H+
5 dissociates
into H+
and
H
.
The
effects
of
deuteration
on
the
structures
and
properties
are
also
investigated.
2
3
a C.
E. Hinkle and A. B. McCoy, J. Phys. Chem. Lett., 1, 562 (2010)
RG03
EINSTEIN A COEFFICIENTS FOR VIBRATION-ROTATIONAL TRANSITIONS OF NO
10 min 2:04
M. GUTIÉRREZ, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332,
USA; J. F. OGILVIE, Escuela de Química and CELEQ, Universidad de Costa Rica, San José 2060, Costa Rica.
Using an algebraic approacha with software for symbolic computation, we calculated the Einstein A coefficients for
vibration-rotational transitions with ∆v = 1 and 2 for NO in its electronic ground state, 2 Π, in substates both Ω = 1/2
and 3/2, up to v = 10. These values will be applicable in an analysis of the chemiluminescence of NO resulting from
exothermic chemical reactions in the gaseous phase.
a J.
F. Ogilvie, The Vibrational and Rotational Spectrometry of Diatomic Molecules, Academic Press, London UK, 1998
301
RG04
15 min 2:16
OZONE PHOTOLYSIS: STRONG ISOTOPOLOGUE/ISOTOPOMER SELECTIVITY IN THE STRATOSPHERE
FABIEN GATTI, CTMM Institut Charles Gerhardt UMR-CNRS 5253 University of Montpellier, France;
STEVE NDENGUE, REMY JOST, Univ. Grenoble 1 / CNRS, LIPhy UMR 5588, Grenoble, F-38041, France;
GABOR HALASZ, AGNES VIBOK, Department of Information Technology, University of Debrecen, P.O.
Box 12, H-4010 Debrecen, Hungary.
Using the visible-UV absorption cross section (Abs. XS) of five ozone isotopologues and an averaged actinic flux, we have
calculated the contribution of the atmospheric ozone photolysis to the oxygen isotope and ozone isotopologue/isotopomer
enrichment. Five ozone isotopologues/isotopomers are considered among which three are symmetric, O16 3 (noted 666),
O16 O17 O16 (676) and O16 O18 O16 (686), and two are asymmetric, O17 O216 (667) and O18 O216 (668). The photolysis rates
of the five ozone isotopologues have been calculated as a function of altitude. The Multi Configuration Time Dependent
Hartree (MCTDH) method and the potential energy surfaces calculates by R. Schinke and coworkers have been used. We
have used experimental actinic fluxes, averaged for latitude and season, for altitudes varying by step of 4km up to 80km.
Below 35km, the contribution of the Hartley band to the photolysis rates is restricted to its low energy range, named the
Huggins band, which has strong isotopologue/isotopomer selectivity and then induces strong enrichment. Consequently,
the isotopologue enrichment’s due to ozone photolysis are strongly dependent of the altitude, with pronounced enrichment
peaks around 35 km, the altitude corresponding to the maximum relative contribution of the Huggins band.
We will also present some new simulations for the simulation of laser-induced quantum dynamics of the electronic and
nuclear motion in the ozone molecule on the attosecond time scale.
RG05
15 min 2:33
LINE SHAPE PARAMETERS FOR CO2 TRANSITIONS: ACCURATE PREDICTIONS FROM COMPLEX ROBERTBONAMY CALCULATIONS
JULIEN LAMOUROUX AND ROBERT R. GAMACHE, Department of Environmental, Earth, and Atmospheric Sciences, University of Massachusetts Lowell, Lowell, MA 01854, USA.
A model for the prediction of the vibrational dependence of CO2 half-widths and line shifts for several broadeners, based
on a modification of the model proposed by Gamache and Hartmanna , is presented. This model allows the half-widths
and line shifts for a ro-vibrational transition to be expressed in terms of the number of vibrational quanta exchanged in
the transition raised to a power p and a reference ro-vibrational transition. Complex Robert-Bonamy calculationsb were
made for 24 bands for lower rotational quantum numbers J ′′ from 0 to 160 for N2 -, O2 -, air-, and self-collisions with
CO2 . In the model a Quantum Coordinate is defined by (c1 ∆ν1 + c2 ∆ν2 + c3 ∆ν3 )p where a linear least-squares fit to
the data by the model expression is made. The model allows the determination of the slope and intercept as a function of
rotational transition, broadening gas, and temperature. From these fit data, the half-width, line shift, and the temperature
dependence of the half-width can be estimated for any ro-vibrational transition, allowing spectroscopic CO2 databases to
have complete information for the line shape parameters.
a R.
b R.
R. Gamache, J.-M. Hartmann, J. Quant. Spectrosc. Radiat. Transfer. 83 (2004), 119.
R. Gamache, J. Lamouroux, J. Quant. Spectrosc. Radiat. Transfer. 117 (2013), 93.
302
RG06
15 min 2:50
AB INITIO CLASSICAL DYNAMICS SIMULATIONS OF CO2 LINE-MIXING EFFECTS IN INFRARED BANDS
JULIEN LAMOUROUXa , JEAN-MICHEL HARTMANN, HA TRAN, Laboratoire Interuniversitaire des
Systèmes Atmosphériques (LISA, CNRS UMR 7583),Université Paris-Est Créteil, Université Paris Diderot,
Institut Pierre-Simon Laplace, 94010 Créteil Cedex, France; MARCEL SNELS, ISAC-CNR, Via del Fosso
del Cavaliere, 100 00133 Rome, Italy; STEFANIA STEFANI and GIUSEPPE PICCIONI, IAPS-IASF, Via del
Fosso del Cavaliere, 100 00133 Rome, Italy.
Ab initio calculations of line-mixing effects in CO2 infrared bands are presented and compared with experiments. The
predictions were carried using requantized Classical Dynamics Molecular Simulations (rCDMS) based on an approach
previously developed and successfully tested for CO2 isolated line shapesb . Using classical dynamics equations, the force
and torque applied to each molecule by the surrounding molecules (described by an ab initio intermolecular potential) are
computed at each time step. This enables, using a requantization procedure, to predict dipole and isotropic polarizability
auto-correlation functions whose Fourier-Laplace transforms yield the spectra. The quality of the rCDMS calculations is
demonstrated by comparisons with measured spectra in the spectral regions of the 3ν3 and 2ν1 + 2ν2 + ν3 Infrared bandsc.
a Support
by the French Agence Nationale de la Recherche (ANR) is gratefully acknowledged.
Hartmann, H. Tran, N. H. Ngo, et al., Phys. Rev. Lett. A 87 (2013), 013403.
c H. Tran, C. Boulet, M. Snels, S. Stefani, J. Quant. Spectrosc. Radiat. Transfer 112 (2011), 925-936.
b J.-M.
RG07
TOWARDS EXPERIMENTAL ACCURACY FROM THE FIRST PRINCIPLES
15 min 3:07
O.L. POLYANSKY, L. LODI, J. TENNYSON, Department of Physics and Astronomy, University College
London, Gower Street, London WC1E 6BT, UK; N.F. ZOBOV, Institute of Applied Physics, Russian Academy
of Sciences, 46 Uljanova St., 603950, Nizhny Novgorod, Russia.
Producing ab initio ro-vibrational energy levels of small, gas-phase molecules with an accuracy of 0.10 cm−1 would
constitute a significant step forward in theoretical spectroscopy and would place calculated line positions considerably
closer to typical experimental accuracy. Such an accuracy has been recently achieveda for the H+
3 molecular ion for line
positions up to 17 000 cm −1 . However, since H+
is
a
two-electron
system,
the
electronic
structure
methods used in this
3
study are not applicable to larger molecules.
A major breakthrough was reported in ref.b , where an accuracy of 0.10 cm−1 was achieved ab initio for seven water
isotopologues. Calculated vibrational and rotational energy levels up to 15 000 cm−1 and J = 25 resulted in a standard
deviation of 0.08 cm−1 with respect to accurate reference data. As far as line intensities are concerned, we have already
achievedc for water a typical accuracy of 1% which supersedes average experimental accuracy.
Our results are being actively extended along two major directions. First, there are clear indications that our results for
water can be improved to an accuracy of the order of 0.01 cm−1 by further, detailed ab initio studies. Such level of
accuracy would already be competitive with experimental results in some situations. A second, major, direction of study is
the extension of such a 0.1 cm−1 accuracy to molecules containg more electrons or more than one non-hydrogen atom, or
both. As examples of such developments we will present new results for CO, HCN and H2 S, as well as preliminary results
for NH3 and CH4 .
a O.L. Polyansky,
A. Alijah, N.F. Zobov, I.I. Mizus, R. Ovsyannikov, J. Tennyson, L. Lodi, T. Szidarovszky and A.G. Csaszar, Phil. Trans. Royal Soc.
London A, 370, 5014-5027 (2012).
b O.L. Polyansky, R.I. Ovsyannikov, A.A. Kyuberis, L. Lodi, J. Tennyson and N.F. Zobov, J. Phys. Chem. A, (in press).
c L. Lodi, J. Tennyson and O.L. Polyansky, J. Chem. Phys. 135, 034113 (2011).
303
RG08
15 min 3:24
HOW MANY VIBRATIONAL LEVELS DOES THE GROUND ELECTRONIC STATE OF THE SODIUM DIMER
SUPPORT?
Cyprus.
Over a decade ago, Raman molecular beam experimentsa were employed to detect the asymptotic vibrational levels of the
ground electronic state of the sodium dimer, and identified υ = 65 as the highest bound vibrational level. This result is in
contrast to the recent predictionb that the vibrational index at dissociation is υ D = 66.9(2). An attempt is made to resolve
this issue, using a direct potential fitting method that considers highly precise term values and a potential energy model
that takes full account of the accurately known long-range dispersion energy coefficients in extrapolating the potential
reliably to the dissociation asymptote. The principal end-product of this procedure, the complete potential energy curve, is
employed to furnish accurate vibrational energies, rotational constants, and centrifugal distortion constants for all bound
vibrational levels. These are then transformed appropriately according to Le Roy-Bernstein long-range theory to yield an
independent WKB estimate of the vibrational index at dissociation.
a A.
b P.
Crubellier, O. Dulieu, F. Masnou-Seeuws, M. Elbs, H. Knöckel, and E. Tiemann, Eur. Phys. J. D 6, 211-220 (1999).
G. Hajigeorgiou, J. Mol. Spectrosc. in press (2013).
Intermission
RG09
15 min 4:00
RESONANCE AND REVIVALS IN QUANTUM ROTORS: COMPARING HALF-INTEGER SPIN AND INTEGER
SPIN
ALVASON ZHENHUA LI, and WILLIAM G. HARTER, Microelectronics-Photonics Program, Department
of Physics, University of Arkansas, Fayetteville, AR 72701.
Quantum rotor wavefunctions based upon Wigner-D matrix are applied to investigate the quantum resonance and revivals
that occur in experimentally accessible spin systems. Interesting physical effects in quantum rotors between half-integer
spin and integer spin systems will be discussed to show effects of symmetry. This study will pave the way for more
rich dynamic behaviors in asymmetric top that include dynamic tunneling between various equivalent energy surface
topography for asymmetric quantum rotors.
A key point is that the quantum revivals in the rotor systems exhibit number-information aspects of surprisingly simple
Farey-sum and Ford-circle geometry. Such quantum dynamic might have applications for quantum information processing
and quantum computing.
RG10
15 min 4:17
EFFECTS OF SUPERFINE STRUCTURE LEVEL-CLUSTER CROSSING ON AMPLITUDE AND PHASE REVIVAL
DYNAMICS: COMPARING TETRAHEDRAL AND OCTAHEDRAL SPHERICAL ROTORS WITH ICOSAHEDRAL
ROTORS
WILLIAM G. HARTER, and ALVASON ZHENHUA LI, Department of Physics, University of Arkansas,
Fayetteville, AR 72701.
Quantum revivals or super-beats are predicted to occur when angularly localized symmetric tops states are free to evolve.
Similar types of dynamics are expected to involve spherical top superfine and superhyperfine level clusters that are labeled
by induced representations of octahedral or tetrahedral symmetries for XY4 , XY6 , and related molecules. A considerably
more complicated set of effects are expected for the icosahedral molecule C60 and its related isotopomers. An important
difference for icosahedral symmetry is that its superfine splitting ratios are most-irrational (Golden-ratio) fractions that
preclude perfect Poincare recurrence of quantum phase while the octahedral splitting ratios are rational.a
a William
Harter and Justin Mitchell, International Journal of Molecular Science, 14, 714 (2013).
304
RG11
EXACT QUANTUM DYNAMICS CALCULATIONS USING PHASE SPACE WAVELETS
15 min 4:34
THOMAS HALVERSON, BILL POIRIER, Department of Chemistry and Biochemistry, and Department of
Physics, Texas Tech University, P.O. Box 41061, Lubbock TX, USA.
In a series of earlier papers, the authors introduced the first exact quantum dynamics method that defeats the exponential
scaling of CPU effort with system dimensionality. The method used a “weylet” basis set (orthogonalized Weyl-Heisenberg
wavelets), combined with a phase space truncation scheme first proposed by M. Davis and E. Heller. Here, we use a
related, but much simpler, wavelet basis consisting of momentum-symmetrized phase space Gaussians. Despite being nonorthogonal, symmetrized Gaussians exhibit collective locality, allowing for effective phase space truncation and the defeat
of exponential scaling. A “universal” and remarkably simple code has been written, which is dimensionally independent,
and which also exploits massively parallel algorithms. The codes have been used to calculate the vibrational spectra of
several molecules of varying dimensionality.
RG12
15 min 4:51
ACHIEVING THE COMPLETE-BASIS LIMIT IN LARGE MOLECULAR CLUSTERS: COMPUTATIONALLY EFFICIENT PROCEDURES TO ELIMINATE BASIS-SET SUPERPOSITION ERROR
RYAN M. RICHARD, JOHN M. HERBERT, Department of Chemistry and Biochemistry, The Ohio State
Previous electronic structure studies that have relied on fragmentation have been primarily interested in those methods’
abilities to replicate the supersystem energy (or a related energy difference) without recourse to the ability of those supersystem results to replicate experiment or high accuracy benchmarks. Here we focus on replicating accurate ab initio
benchmarks, that are suitable for comparison to experimental data. In doing this it becomes imperative that we correct our
methods for basis-set superposition errors (BSSE) in a computationally feasible way. This criterion leads us to develop
a new method for BSSE correction, which we term the many-body counterpoise correction, or MBn for short. MBn is
truncated at order n, in much the same manner as a normal many-body expansion leading to a decrease in computational
time. Furthermore, its formulation in terms of fragments makes it especially suitable for use with pre-existing fragment
codes. A secondary focus of this study is directed at assessing fragment methods’ abilities to extrapolate to the complete
basis set (CBS) limit as well as compute approximate triples corrections. Ultimately, by analysis of (H2 O)6 and (H2 O)10 F−
systems, it is concluded that with large enough basis-sets (triple or quad zeta) fragment based methods can replicate high
level benchmarks in a fraction of the time.
RG13
15 min 5:08
VIBRATIONAL ANYLASIS ON I(H2 O) and I(D2 O) SPECTRA
−
−
MENG HUANG and ANNE B. McCOY, Department of Chemistry, The Ohio State University, Columbus,
Ohio 43210.
Hydrated halide clusters provide good systems for investigating the effect of the intramolecular hydrogen-bond on the
spectrum of ions and molecules. In this work, the vibrational spectra of I(H2 O)− and I(D2 O)− were studied. We focused
on the couplings between the two O-H stretch modes and the in-plane bending mode, which is the frustrated rotation of
the water molecule in the plane of the complex. A reduced-dimensional analysis with these three modes was developed
to investigate the effect of the couplings on the spectra. The model potential in the analysis was obtained from ab initio
calculation with MP2/aug-cc-pVTZ-PP level of method and basis set. The doublet structure of the O-H stretch mode in the
spectrum was attributed to the tunneling splitting from the in-plane bending mode double-well potential energy surface.
305
RG14
AB-INITIO STUDY OF THE GROUP 2 HYDRIDE ANIONS
10 min 5:25
JOE P. HARRIS, TIMOTHY G. WRIGHT and DANIEL R. MANSHIP, School of Chemistry, University Park,
University of Nottingham, NG7 2RD, United Kingdom.
The beryllium hydride (Be···H)- dimer has recentlya been shown to be surprisingly strongly bound, with an electronic
structure which is highly dependent on internuclear separation. At the equilibrium distance, the negative charge is to
be found on the beryllium atom, despite the higher electronegativity of the hydrogen. The current study expands this
investigation to the other Group 2 hydrides, and attempts to explain these effects.
a M.
Verdicchio, G. L. Bendazzoli, S. Evangelisti, T. Leininger J. Phys. Chem. A, 117, 192, (2013)
RG15
15 min 5:37
ACCURATE INTERMOLECULAR INTERACTIONS AT DRAMATICALLY REDUCED COST AND A MANY-BODY
ENERGY DECOMPOSITION SCHEME FOR XPol+SAPT
KA UN LAO and JOHN M. HERBERT, Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH 43210.
An efficient, monomer-based electronic structure method is introduced for computing non-covalent interactions in molecular and ionic clusters. It builds upon our “explicit polarization" (XPol) with pairwise-additive symmetry-adapted perturbation theory (SAPT) using the Kohn-Sham (KS) version of SAPT, but replaces the problematic and expensive sumover-states dispersion terms with empirical potentials. This modification reduces the scaling from O(N 5 ) to O(N 3 ) and
also facilitates the use of Kohn-Sham density functional theory (KS-DFT) as a low-cost means to capture intramolecular electron correlation. Accurate binding energies are obtained for benchmark databases of dimer binding energies, and
potential energy curves are also captured accurately, for a variety of challenging systems. As compared to traditional DFTSAPT or SAPT(DFT) methods, it removes the limitation to dimers and extends SAPT-based methodology to many-body
systems. For many-body systems such as water clusters and halide–water cluster anions, the new method is superior to established density-functional methods for non-covalent interactions. We suggest that using different asymptotic corrections
for different monomers is necessary to get good binding energies in general, as DFT-SAPT or SAPT(DFT), especially for
hydrogen-bonded complexes. We also introduce a decomposition scheme for the interaction energy that extends traditional
SAPT energy decomposition analysis to systems containing more than two monomers, and we find that the various energy
components (electrostatic, exchange, induction, and dispersion) are in very good agreement with high-level SAPT benchmarks for dimers. For (H2 O)6 , the many-body contribution to the interaction energy agrees well with that obtained from
traditional Kitaura-Morokuma energy decomposition analysis.
306
RH. DYNAMICS
Chair: GEOFFREY DUXBURY, University of Strathclyde, Bearsden, United Kingdom
RH01
15 min 1:30
TORSION-INVERSION TUNNELING PATTERNS IN THE CH-STRETCH VIBRATIONALLY EXCITED STATES OF
THE G12 MOLECULES
MAHESH B. DAWADI, RAM S. BHATTA and DAVID S. PERRY, Department of Chemistry, The University
of Akron, Akron OH, 44325.
Torsion-inversion tunneling models have been developed for CH-stretch vibrationally excited states in G12 molecules, including 2-methylmalonaldehyde (2-MMA), 5-methyltropolone (5-MT), and methylamine. These models are extensions of
the group theoretical approach of Hougena and the internal coordinate model of Wang and Perryb in which the inversion
motion is included in addition to the torsion and the small-amplitude (e.g., CH stretch) vibrations. The present models incorporate torsion-inversion tunneling parameters h2V and h3V , respectively and a number of low-order terms couplings to
the CH-stretch vibrations. Of the three methyl CH stretch vibrations, Model I includes only the two asymmetric stretches
that correlate to the E-type degenerate CH stretch in a symmetric rotor; Model II includes all three. The models yield
the torsion-inversion tunneling patterns of the four symmetry species, A, B, E1 and E2 , in the CH-stretch excited states.
The principal results are as follows. (i) Both models and each of the coupling terms considered yield the same tunneling
patterns, which are different in the asymmetric CH stretch excited states as compared to those in the ground state. (ii) In
Model I, the magnitude of the tunneling splittings in the two asymmetric CH stretch excited states is exactly half of that in
the ground state. (iii) In Model II, the relative magnitude of these splittings depends on the ratio |µ|/(|h2V |+|h3V |) where
µ is the torsion-inversion-vibration coupling parameter. This ratio varies from 3 to 308 across the series methanol, methylamine, 2-methylmalonaldehyde and 5-methyltropolone, with a consequent variation in the magnitude of the tunneling
splittings.
a J.
T. HougenJ. Mol. Spectrosc. 207, 60, (2001).
Wang and D. S. PerryJ. Chem. Phys. 109, 10795, (1998).
b X.
RH02
15 min 1:47
COUPLING OF THE C-H STRETCH TO LARGE-AMPLITUDE TORSION AND INVERSION MOTIONS: COMPARISON OF CH3 CH2 . , CH3 OH2 + AND CH3 NH2
RAM S. BHATTA, Department of Polymer Science and Department of Chemistry, The University of Akron;
DAVID S. PERRY, Department of Chemistry, The University of Akron, OH 44325.
In each of the title molecules, torsional and inversion tunneling occurs between six equivalent minima. Coupling of these
degrees of freedom to the CH stretch occurs via variation of the C-H stretching force constants as a function of the torsional
(α) and inversion (τ ) angles. Maps of the couplings have been computed at the MP2/6-311++G(3df,2p) level. Both the
single bond CH stretch force constants and the bilinear couplings between CH bonds are presented as a function of α and
τ . Although the torsional barriers differ by more than a factor of 20, the torsion-inversion-vibration coupling patterns are
very similar for CH3 NH2 and CH3 CH2 . . On the other hand, the torsion-inversion-vibration coupling in the charged species
CH3 OH2 + is much weaker.
307
RH03
15 min 2:04
HYDROGEN ABSTRACTION FROM METHANE BY BROMINE AND CHLORINE RADICALS: A DYNAMICS
COMPARISON
ANDREW E. BERKE, ETHAN H. VOLPA, F. FLEMING CRIM, Chemistry Department, University of Wisconsin - Madison, Madison, Wisconsin 53706.
The abstraction of H or D from methane and its isotopologues by H, F, or Cl radicals has long been the poster child for gas
phase bimolecular reaction dynamics experiments. Recently, our group has successfully carried out a reaction dynamics
study of the hydrogen abstraction from CH4 by Br radicals to produce CH3 and HBr. To our knowledge, this is the first
successful attempt at adding bromine to the repertoire of H abstraction collision partners in a molecular beam study. As
a point of comparison for our Br experiments, we have also revisited the well understood H-abstraction from CH4 by Cl.
In the Br system, we see dramatic vibrational mode selectivity similar to that observed in previous studies done on the
Cl analog system. However, due to the large barrier height of the H-abstraction by Br ( 4500 cm−1 ) compared to that of
abstraction by Cl ( 1200 cm−1 ), the manifestations of the mode selectivity are markedly different in the two systems.
RH04
A NEW APPROACH TOWARD TRANSITION STATE SPECTROSCOPY
15 min 2:21
KIRILL PROZUMENT, RACHEL G. SHAVER, MONIKA A. CIUBA, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139; JOHN S. MUENTER, Department of Chemistry,
University of Rochester, Rochester, NY 14627; G. BARRATT PARK, Department of Chemistry, Massachusetts
Institute of Technology, Cambridge, MA 02139; JOHN F. STANTON, Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, TX 78712; HUA GUO, Department of Chemistry, University
of New Mexico, Albuquerque, NM 87131; BRYAN M. WONG, Materials Chemistry Department, Sandia National Laboratories, Livermore, CA 94550; DAVID S. PERRY, Department of Chemistry, The University of
Akron, Akron, OH 44325; ROBERT W. FIELD, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139.
Chirped-Pulse Millimeter-Wave (CPmmW) rotational spectroscopy provides a new class of information that is a step
toward Transition State spectroscopy. Our CPmmW studies of the vinyl cyanide (acrylonitrile) photolysis reaction at 193
nm provide information about the vibrational state population distribution of the HCN, HNC products. These populations
encode information about the structure of the transition state(s) traversed by the parent molecule as it dissociates. Two of
the expected products of the reaction, vinylidene and local-bender levels of acetylene, have, however, escaped detection.
The feasibility of CPmmW schemes for characterizing vinylidene-acetylene isomerization is discussed. The authors thank
the Department of Energy for support.
308
RH05
15 min 2:38
PHOTODISSOCIATION DYNAMICS OF VINYL CYANIDE STUDIED BY CHIRPED-PULSE MILLIMETER-WAVE
SPECTROSCOPY OF HCN AND HNC PRODUCTS
KIRILL PROZUMENT, RACHEL G. SHAVER, JOSHUA H. BARABAN, G. BARRATT PARK, Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139; ARTHUR G. SUITS, Department of Chemistry, Wayne State University, Detroit, MI 48202; JOHN S. MUENTER, Department of
Chemistry, University of Rochester, Rochester, NY 14627; ROBERT W. FIELD, Department of Chemistry,
Massachusetts Institute of Technology, Cambridge, MA 02139.
Vinyl cyanide 193 nm photodissociation has been studied using Chirped-Pulse Millimeter-Wave (CPmmW) spectroscopy.
J = 0 − 1 transitions of more than 30 vibrationally excited states of the HCN and HNC products have been recorded and
assigned within the 7 GHz wide chirp range. Bending excitations of HCN up to v2 = 14, leading toward the HCN ↔ HNC
isomerization transition state, are detected and interpreted in terms of their electric quadrupole, (eQq)N , and rotational,
Bv , constants. The photolysis reaction transition states were probed using both normal vinyl cyanide, CH2 =CHCN, and
its singly-deuterated isotopologue, CH2 =CDCN. The observed difference in the vibrational population distribution (VPD)
obtained from the integrated intensities of the HCN and DCN products from the CH2 =CHCN vs. CH2 =CDCN photolysis
reactions, suggests the relative unimportance of the three-center elimination mechanism for HCN production. On the other
hand, the similarity in the observed VPD and overall intensities of HCN from CH2 =CHCN and CH2 =CDCN photolysis
suggests four-center elimination as the major mechanism leading to the HCN product. Additional J − (J + 1) transitions
would be required to characterize both the vibrational and the rotational state distributions of the products, which would
permit more complete characterization of the transition state(s). The authors thank the Department of Energy, and KP
thanks the ACS Petroleum Research Fund for their support of this work.
RH06
15 min 2:55
ENERGY TRANSFER AND LASING OF THE LOWER Ar(3p 4p) STATES IN Ar and He
5
JIANDE HAN and MICHAEL C. HEAVEN, Department of Chemistry, Emory University, Atlanta, GA 30322.
Pulsed lasing from optically pumped noble gas atoms has been demonstrated previously in our laboratory. The lasing relied
on a three level scheme, which involved the two lowest energy states of the np5 (n+1)p configuration and the lowest energy
state of the np5 (n+1)s configuration 3 P2 . Population inversion was achieved using collisional relaxation by helium or argon
at pressures near 1 atm. State-to-state energy transfer rate constants are required for modeling these systems. In this study,
we have measured the energy transfer and quenching rate constants for the lower Ar(3p5 4p) states in collisions with Ar and
He. The excited states were populated by pulsed laser excitation of metastable Ar atoms. The metastables were generated
by a pulsed electrical discharge. Kinetic processes were interrogated using time-resolved laser induced fluorescence and
dispersed fluorescence techniques. For Ar* in collision with Ar, our measured rate constants are in reasonable agreement
with previously reported values. For Ar* with He, the rate constants had not been reported previously. We have also
investigated the possibility of forming an Ar laser buffered with He or Ar and pumped by a CW diode laser. The lasing
experiments will be reported, and the application of the measured rate constants to modeling the lasing system will be
described.
309
RH07
GRAVITATON WAVE AND GRAVITATIONAL-PHOTON INTERACTION
15 min 3:12
KHOLMURAD KHASANOV, Lomonosov Moscow State University, Gas and Wave Dynamics Department,
Moscow, Russia, 119991, GSP-1, 1 Leninskie Gory Str.Email: [email protected].
Gravitation waves and gravitational-photon interaction with high energy photons emission is found experimentally. Supercompressibility phenomenon was studied. Spectral investigations of supersonic jets and incandescent nichrome thread and
wolfram spiral were studied. The shifting of the emission spectrum was detected depending on vector of gravity. The
increasing frequency of light emitted against gravity vector is measured. Uneven along the spectrum character of intensity
increasing is found. Generation of short-wavelength component of the spectrum is observed in case of more power of heating. The measurements show that presented interactions have resonance nature. Our experiments demonstrate the existence
resonance nature. Our experiments demonstrate the gravitation wave and generation and existence of gravitational-photon
interactions.
From left to right:
Fig. 1-2. Visualization of the gravitation wave.
Fig. 3-5. Gravitational-photon interaction in HF field.
Intermission
RH08
15 min 3:45
PROBING CHEMICAL DYNAMICS WITH HIGH RESOLUTION SPECTROSCOPY: CHIRPED-PULSE FOURIERTRANSFORM MICROWAVE SPECTROSCOPY COUPLED WITH A HYPERTHERMAL SOURCE
VANESA
VAQUERO
VARA
,
DEEPALI
N.
MEHTANATHANAEL M. KIDWELL,
HURT, JOSEPH A. KORN, BRIAN C. DIAN, and TIMOTHY S. ZWIER, Department of Chemistry,
Purdue University, West Lafayette, IN 47907-2084.
Chirped-pulse Fourier-transform microwave (CP-FTMW) spectroscopy has proven to be a well-suited technique for the
rapid study and spectral identification of molecular species due to its ultra-broadband capability and excellent specificity
to molecular structure from high-resolution rotational transitions. This talk will describe initial results from combining
CP-FTMW detection with a hyperthermal nozzle source. This source has the advantage of producing traditionally high
thermal product densities in a pulsed supersonic expansion with a short contact time compared to conventional pyrolysis.
Used in tandem, CP-FTMW spectroscopy and the hyperthermal nozzle in a supersonic expansion is a powerful method
that can produce and detect changes in conformation and isomer populations, and characterize important intermediates on
the reaction surface of a precursor. In particular, we show its utility to provide insight into the unimolecular decomposition
pathways of model lignin compounds and alternative biofuels. Preliminary results will be discussed including spectroscopic evidence for formation of cyclopentadienone in the pyrolysis of a lignin derivative guaiacol (o-methoxyphenol).
310
RH09
15 min 4:02
J-SPECIFIC DYNAMICS IN AN OPTICAL CENTRIFUGE USING TRANSIENT IR SPECTROSCOPY
MATTHEW J. MURRAY, QINGNAN LIU, CARLOS TORO and AMY S. MULLIN, Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742.
Quantum state-specific dynamics are reported for a number of CO2 rotational states in an optical centrifuge. The optical
centrifuge results from combining oppositely-chirped ultrafast laser pulses and spinning CO2 molecules into extremely
high rotational states with J≈220. Collisions of centrifuged molecules induce depletion of population from low-J states
(J=0 and 36) and lead to appearance of population in high J states (J=36, 54 and 76). Transient Doppler-broadened line
profiles for individual CO2 states reveal that the depletion populations have narrow velocity distributions with translational
temperatures significantly colder than 300 K. Molecules that appear in the higher rotational states have broad velocity
distributions, showing that both rotational and translational energy are imparted in collisions of the centrifuged molecules.
These results show that substantial amounts of angular momentum persist after many collisions and that translational
energy exchange continues for several thousand collisions.
RH10
15 min 4:19
OBSERVATION OF NEW DYNAMICS IN THE STATE-RESOLVED COLLISIONAL RELAXATION OF HIGHLY
EXCITED MOLECULES
GERALDINE O. ECHEBIRI, MATTHEW SMARTE, WENDELL W. WALTERS, JILL M. CLEVELAND,
CHRISTINE MCCARL, ALICE KUNIN and AMY S. MULLIN, Department of Chemistry and Biochemistry,
University of Maryland, College Park, MD 20742.
The dynamics of collisional deactivation of highly energized molecules, pyrazine-h4 and pyrazine-d4, by HCl molecules
at 300 K show evidence of a new mechanism for collisional energy transfer. Highly vibrationally excited (Evib = 37,900
cm−1 ) pyrazine-h4 and pyrazine-d4 molecules are produced in separate experiments by pulsed excitation with the fourth
harmonic output of a Nd:YAG laser at λ = 266 nm. Collisions between the energized isotopes and HCl molecules are
monitored by measuring the nascent transient IR absorption of scattered HCl in individual rotational states. The results
indicate that HCl molecules are scattered with a gain in rotational and translational energy, but the largest recoil energies
are observed for the lowest rotational energy states of HCl. This behavior is opposite to that seen for other bath molecules
including DCl and CO2 . The results point to differences in intermolecular interactions between the energy donor and
acceptor molecules as contributing factors to the observed differences in the mechanism of energy transfer.
RH11
10 min 4:36
TIME RESOLVED INFRARED EMISSION FROM VIBRATIONAL EXCITED ACETYLENE FOLLOWING SUPER
ENERGY TRANSFER COLLISIONS WITH HOT HYDROGEN
J. M. SMITH, M. NIKOW, J. MA AND H.L. DAI, Department of Chemistry, Temple University, Philadelphia,
Pennsylvania 19122, USA.
Can a molecule be activated with large amounts of energy transferred in a single collision between an atom and a molecule?
If so, this type of collision will greatly affect molecular reactivity and equilibrium in systems including combustion where
abundant hot atoms exist. Conventional expectation of translation to vibration (T-V) energy transfer is that probability
decreases exponentially with energy transferred. We show, however, that in collisions between a pair of atom/molecule
for which chemical reactions may occur, such as between a hyperthermal H atom and an ambient acetylene molecule, (TV) energy transfer occurs with surprisingly high efficiency through chemical complex formation. Time-resolved infrared
emission observations reveal that collisions between H atoms moving with 60 kcal/mole energy and acetylene molecules
result in transfer of up to 70% of this energy into vibrational degrees of freedom. These experimental results are further
supported by state of the art quasi-classical trajectory calculations performed by Bowman and coworkers.
311
RH12
15 min 4:48
TIME-RESOLVED IR-IR DOUBLE RESONANCE FOR THE ν4 and 2ν4 −ν4 VIBRATION-ROTATION TRANSITIONS
OF CH3 F
YUSUKE OKABAYASHI, JIAN TANG, YUKI MIYAMOTO, KENTAROU KAWAGUCHI, Graduate
School of Natural Science and Technology, Okayama University, 3-1-1 Tsushima-Naka, Okayama 700-8530,
Japan.
Time-resolved double resonance (TRDR) method has been used to study the rotational and vibrational relaxiation for a
long time. However, the study of IR-IR TRDR in the 3µm region has been very limited due to the lack of powerful tunable
IR lasers in this region. In the present study, we used a tunable pulsed OPO IR laser (6 mJ@6 ns, ∼0.2 cm−1 linewidth)
and a tunable cw-OPO IR laser (up to 200 mW, ∼3 MHz linewidth) both in the 3µm region to study the IR-IR TRDR for
the ν4 and 2ν4 − ν4 vibrational bands of CH3 F.
The pulsed IR laser pumps CH3 F from the ground state to a certain rotational level (J, K) of v4 = 1, and the cw IR laser
probes this (J, K) level by the 2ν4 − ν4 ladder transition. A time profile for the transition intensity of the probe line gives
the T1 relaxiation time for the (J, K) level of v4 = 1. The pressure dependence of T1 for various (J, K) levels of v4 = 1
was obtained, which can be compared with the linewidth measurementa for the ν4 band of CH3 F.
a A.
G. Cartlidge and R. J. Butcher, J. Phys. B: At. Mol. Opt. Phys. 23, 2083 (1990).
RH13
VIBRATIONAL ENERGY RELAXATION OF CHOLOROIODOMETHANE IN COLD ARGON
15 min 5:05
AMBER JAIN and EDWIN L. SIBERT III, Department of Chemistry and Theoretical Chemistry Institute,
University of Wisconsin-Madison, WI 53706.
Electronically exciting the C-I stretch in the molecule chloroiodomethane CH2 ClI embedded in a matrix of argon at 12K
can lead to an isomer, iso-chloroiodomethane CH2 Cl-I, that features a chlorine iodine bond.a By temporally probing the
isomer at two different frequencies of 435 nm and 485 nm, multiple timescales for isomerization are inferred. To gain further mechanistic insights into this process we have studied the isomerization theoretically using molecular dynamics. Two
and three low frequency modes (C-Cl-I bend, Cl-I stretch and C-Cl stretch) are included in the model. The experiment is
simulated by equilibrating the molecule in the parent configuration and providing an energy of 37,500 cm−1 , corresponding to the electronic excitation of the C-I stretch. Subsequent time evolution of the classical trajectories is monitored, and
the decay rates of energy are compared to the experimental spectroscopy results. Varying different parameters related to
the potential energy surface can lead to different results and their implications to the energy flow are discussed. The decay
rates in the isomer well are also compared to the classical Landau Teller theory.
a T.
J. Preston, M. Dutta, B. J. Esselman, A. Kalume, L. George, R. J. McMahon, S. A. Reid, and F. F. Crim, J. Chem. Phys. 135, 114503 (2011)
RH14
15 min 5:22
DETERMINATION OF DIFFERENTIAL CROSS SECTIONS OF THE STATE-TO-STATE INELASTIC COLLISIONS
IN BULBS. A THREE-DIMENSIONAL SLICED FLUORESCENCE IMAGING STUDY
KUO-MEI CHEN, Department of Chemistry, National Sun Yat-sen University, Kaohsiung, Taiwan, Republic
of China.
Differential cross sections of the state-to state inelastic collisions can be determined by the three-dimensional sliced fluorescence imaging techniques in a flow cell. An optical-optical double resonance excitation scheme is employed in the state
selection and detection of one of the colliding species. From the collision-induced fluorescence images, a double Legendre
moment analysis framework is utilized to extract the state-to-state inelastic differential cross sections of CN in the A state
with He.
312
RH15
ION IMAGING STUDIES OF CH2 I2 PHOTODISSOCIATION AT 248 NM
15 min 5:39
JULIA H. LEHMAN, HONGWEI LI and MARSHA I. LESTER, Department of Chemsitry, University of
Pennsylvania, Philadelphia, PA 19104-6323.
CH2 I2 plays an important role in atmospheric chemistry as a significant natural source of organohalide compounds. The
photodissociation dynamics of CH2 I2 in the ultraviolet range of 277-305 nm via the two lowest B1 excited states has been
well studied using one-color velocity map ion imaging (VMI) and photofragment translational spectroscopy. In this twocolor experimental study, CH2 I2 is photodissociated by 248 nm via the B2 or A1 excited states to give rise to CH2 I and I
(2 P3/2 ) or I∗ (2 P1/2 ). The iodine atoms are then state selectively ionized using a (2+1) resonance-enhanced multiphoton
ionization process near 310 nm and detected by VMI. Preliminary results show about 85% of the available energy is being
funneled into the internal energy of the CH2 I fragment, consistent with prior infrared emission results of Baughcum and
Leone.a The anisotropy parameter derived from the image indicates this is a fast dissociation process and reflects the
character of the electronic transition. The internal energy distribution of the CH2 I fragment is of particular interest because
of its subsequent reaction with O2 in a near thermo-neutral reaction to produce the smallest Criegee intermediate, CH2 OO.
We anticipate that the internal energy contained in CH2 I will likely be carried into CH2 OO.
a S.
L. Baughcum and S. R. Leone, J. Chem. Phys. 72, 6531 (1980).
313
RI. ATMOSPHERIC SPECIES
Chair: YEN-CHU HSU, Academia Sinica, Taipei, Taiwan
RI01
HITRAN2012: DOWN TO EARTH
15 min 1:30
The HITRAN2012a database is now officially released.
As usual, the assembly of the HITRAN database exemplifies the efficiency and necessity of worldwide scientific collaborations. It is a remarkable effort of experimentalists, theoreticians and atmospheric scientists who measure, calculate, and
validate the HITRAN data. The line-by-line lists for almost all of the 42 HITRAN molecules were updated in comparison
with the previous compilation (HITRAN2008b). The scope of the updates ranges from corrections to the representations
of quantum assignments to complete replacements of the lists and introduction of new molecules and isotopologues. Some
of the most important updates, relevant to the studies of terrestrial atmosphere such as for water vapor, CO2 , molecular
oxygen, etc, will be presented in more detail. The HITRAN2012 database now provides alternative line-shape representations for a number of molecules, whereas previous editions of database provided parameters only for Voigt profile. In
addition, new as well as improved sets of cross-section data have been added. Finally, collision-induced absorption (CIA)
parameters were introduced to the database for the first time. The new edition of the database is a substantial step forward
to improve retrievals of the atmospheric constituents in comparison with previous editions.
Note that another talk will be given in the "Planetary Atmospheres" session describing the new features in HITRAN2012
that will aid remote sensing of planetary atmospheres.
a The
b L.
HITRAN database is supported by the NASA Earth Observing System (EOS) under the grant NAG5-13534.
S. Rothman, I. E. Gordon, et al. "The HITRAN 2008 molecular spectroscopic database," JQSRT, 110, 532-572 (2009).
RI02
15 min 1:47
CAVITY-ENHANCED, FREQUENCY-AGILE RAPID SCANNING (FARS) SPECTROSCOPY: MEASUREMENT
PRINCIPLES
JOSEPH T. HODGES, DAVID A. LONG, GAR-WING TRUONG, KEVIN O. DOUGLASS, STEPHEN E.
MAXWELL, ROGER VAN ZEE, and DAVID F. PLUSQUELLIC, National Institute of Standards and Technology, 100 Bureau Drive, Gaithersburg, MD 20899, USA.
We present the principles of frequency-agile, rapid scanning (FARS) spectroscopy, a new technique for high-bandwidth,
cavity-enhanced, laser absorption measurements. This method enables a visible or near-infrared probe laser beam to be
frequency tuned over several tens of GHz using a microwave source, a waveguide phase modulator and a filter cavity. For
the types of cavity-enhanced methods discussed here, the optical resonator itself is used to select a single sideband of the
modulated laser spectrum, obviating the need for a separate filter cavity. FARS offers several important advantages over
conventional cw laser tuning methods based on thermal or mechanical methods. These include, high speed tuning with
sub-ms switching times, the ability to select arbitrary frequency steps or chirp rates, and the realization of a spectrum
detuning axis with sub-kHz level precision. We discuss how FARS can be applied to cavity ring-down spectroscopy and
other cavity-enhanced methods to enable rapid and accurate measurements of line parameters and to give noise-equivalent
absorption coefficients at the 10−12 cm−1 Hz−1/2 level.
314
RI03
15 min 2:04
CAVITY-ENHANCED, FREQUENCY-AGILE RAPID SCANNING (FARS) SPECTROSCOPY: EXPERIMENTAL REALIZATIONS AND MEASUREMENT RESULTS
DAVID A. LONG, GAR-WING TRUONG, ROGER VAN ZEE, DAVID F. PLUSQUELLIC, and JOSEPH T.
HODGES, National Institute of Standards and Technology, 100 Bureau Drive, Gaithersburg, MD 20899, USA.
We present a series of experimental realizations of cavity-enhanced, frequency-agile rapid scanning (FARS) spectroscopy
using distributed feedback diode lasers, external cavity diode lasers, and ultra-narrow linewidth fiber lasers. FARS offers
a scanning rate which is limited only by the cavity response time itself as well as a microwave-level frequency axis.
Finally, it allows for an absorption sensitivity which is one of the highest ever reported. These realizations offer a range of
applications from low-cost field measurements of trace gases to laboratory-based metrology.
RI04
15 min 2:21
PERFORMANCE OF A CRYOGENIC 21 METER-PATH COPPER HERRIOTT CELL VACUUM COUPLED TO A
BRUKER 125HR SYSTEM
ARLAN W. MANTZ, Dept. of Physics, Connecticut College, New London, CT 06320; KEEYOON SUNG,
TIMOTHY J. CRAWFORD, SHANSHAN YU, LINDA R. BROWN, Jet Propulsion Laboratory, California
Institute of Technology, 4800 Oak Grove Dr.,Pasadena, CA 91109; MARY ANN H. SMITH, Science Directorate, NASA Langley Research Center, Hampton, VA 23681; V. MALATHY DEVI, D. CHRIS BENNER,
Dept. of Physics, The College of William and Mary, Williamsburg, VA 23187.
Accurate modeling of planetary atmospheres requires a detailed knowledge of the temperature and pressure dependence
of spectroscopic line parameters of atmospheric molecules. With this requirement in mind, a new Herriott cell having a
21 meter folded absorption path was designed and fabricated with Oxygen-Free High Conductivity (OFHC) copper body
and gold coated OFHC copper mirrors to operate for the first time with a broad-band Fourier transform spectrometer. The
cell, enclosed in an isolated vacuum box, is cooled by a CTI Cryogenics, Inc. model 1050 closed-cycle helium refrigerator
which also cryopumps the vacuum box. The temperature of the cell is monitored by a silicon temperature sensor and
regulated by a Lakeshore model 331 temperature controller.
The new cell system was integrated to the JPL Bruker model 125HR interferometer with transfer optics which are fully
evacuated to 12 mTorr (the pressure inside the interferometer). The optics were through-put matched for entrance apertures
smaller than 2 mm. The system has successfully operated for several months at gas sample temperatures between 75 and
250 K with extremely good stability to obtain spectra of methane, carbon dioxide, and oxygen bands between 0.76 and
3 µm. We present the characterization and performance of the Herriott cell system and preliminary analyses of newly
recorded spectra. a
a Research described in this paper was performed at Connecticut College, the Jet Propulsion Laboratory, California Institute of Technology, NASA
Langley Research Center, and The College of William and Mary under contracts and cooperative agreements with the National Aeronautics and Space
Administration.
315
RI05
15 min 2:38
FREQUENCY-COMB REFERENCED, SUB-DOPPLER SPECTROSCOPY OF HOT BANDS OF ACETYLENE IN
THE REGION OF THE ν1 + ν3 COMBINATION BAND
CHRISTOPHER P. MCRAVEN, Chemistry Department, Brookhaven National Laboratory, Upton, New York
11973; MATTHEW J. CICH, SALVATORE M. CAIOLA, Department of Chemistry, Stony Brook University,
Stony Brook, New York 11794; TREVOR J. SEARSa , Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973; GREGORY E. HALL, Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973.
To take full advantage of recent improvements in the accuracy obtained in collision-induced absorption line shape measurements of the acetylene ν1 + ν3 combination band, independent and accurate knowledge of the positions of weaker,
overlapping hot band transitions is required. We have used cavity-enhanced saturation-absorption spectroscopy together
with a frequency-comb referenced, extended cavity diode laser to determine Doppler-free transition frequencies for the ν4
and ν5 hot band transitions in this region . A laser intensity dependent asymmetry in the sub-Doppler saturation line shape
is observed, and will be discussed in terms of the intra-cavity beam geometry.
Acknowledgments: Work at Brookhaven National Laboratory was carried out under Contract No. DE-AC02-98CH10886
with the U.S. Department of Energy and supported by its Office of Basic Energy Sciences, Division of Chemical Sciences,
Geosciences and Biosciences.
a also:
Department of Chemistry, Stony Brook University, Stony Brook, New York 11794
RI06
15 min 2:55
DIAGNOSTIC CHEMICAL ANALYSIS OF EXHALED HUMAN BREATH USING A NOVEL SUBMILLIMETER/TERAHERTZ SPECTROSCOPIC APPROACH
ALYSSA M. FOSNIGHT, BENJAMIN L. MORAN, DANIELA R. BRANCO, JESSICA R. THOMAS, IVAN
R. MEDVEDEV, Department of Physics, Wright State University, 3640 Colonel Glenn Highway, Dayton, OH
45435, USA.
As many as 3000 chemicals are reported to be found in exhaled human breath. Many of these chemicals are linked to
certain health conditions and environmental exposures. Present state of the art techniques used for analysis of exhaled
human breath include mass spectrometry based methods, infrared spectroscopic sensors, electro chemical sensors and
semiconductor oxide based testers. Some of these techniques are commercially available but are somewhat limited in their
specificity and exhibit fairly high probability of false alarm. Here, we present the results of our most recent study which
demonstrated a novel application of a terahertz high resolutions spectroscopic technique to the analysis of exhaled human
breath, focused on detection of ethanol in the exhaled breath of a person which consumed an alcoholic drink. This technique
possesses nearly “absolute” specificity and we demonstrated its ability to uniquely identify ethanol, methanol, and acetone
in human breath. This project is now complete and we are looking to extend this method of chemical analysis of exhaled
human breath to a broader range of chemicals in an attempt to demonstrate its potential for biomedical diagnostic purposes.
RI07
15 min 3:12
TERAHERTZ CHEMICAL ANALYSIS OF EXHALED HUMAN BREATH - BROAD ESSAY OF CHEMICALS
DANIELA R. BRANCO, ALYSSA M. FOSNIGHT, JESSICA R. THOMAS, IVAN R. MEDVEDEV, Department of Physics, Wright State University, 3640 Colonel Glenn Highway, Dayton, OH 45435, USA.
Approximately 3000 chemicals are thought to be present in human breath. Of these chemicals, many are considered typical
of exhaled air. Yet, others can allude to different disease pathologies. The detection of chemicals in breath could have many
practical purposes in medicine and provide a noninvasive means of diagnostics. We have previously reported on detection
of ethanol, methanol, and acetone in exhaled human breath using a novel sub-millimeter/THz spectroscopic approach.
This paper reports on our most recent study. A tentative list has been made of approximately 20 chemicals previously
found in breath using other methods. Though many of these chemicals are only expressed in samples from donors with
certain pathologies, at the time of this submission we are able to detect and quantitatively measure acetaldehyde and
dimethyl sulfide in the breath of several healthy donors. Additional tentatively identified chemicals have been seen using
this approach. This presentation will explain our experimental procedures and present our most recent results in THz breath
analysis. Prospects, challenges and future plans will be outlined and discussed.
316
Intermission
RI08
SF6 : THE FORBIDDEN BAND UNVEILED
15 min 3:45
V. BOUDON, Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS–Université de Bourgogne, 9 Av. A. Savary, BP 47870, F-21078 Dijon Cedex, France; L. MANCERON, Laboratoire de Dynamique, Interactions et Réactivité, CNRS UMR 7075, 4 Place Jussieu, F-75252 Paris Cedex, France; F.
KWABIA-TCHANA, Laboratoire Interuniversitaire des Systèmes Atmosphériques, UMR CNRS 7583, Université Paris-Est Créteil et Université Paris-Diderot, 61 Avenue du Général de Gaulle, 94010 Créteil Cedex,
France; P. ROY, Ligne AILES – Synchrotron SOLEIL, L’Orme des Merisiers, F-91192 Gif-sur-Yvette, France.
Sulfur hexafluoride (SF6 ) is a greenhouse gas of anthropogenic origin, whose strong infrared absorption in the ν3 S–F
stretching region near 948 cm−1 induces a global warming potential 23900 times bigger than CO2 . This heavy species features many hot bands at room temperature (at which the ground state population is only 30 %), especially those originating
from the v6 = 1 state. Unfortunately, the ν6 band itself (near 347 cm−1 ) being, in first approximation, both infrared and
Raman inactive, no reliable information could be obtained about it up to now. A long time ago, some authors suggesteda
that this band may be slightly activated through Coriolis interaction and may appear as a very faint band, with an integrated
intensity about 2 millionths of that of ν3 . Using a new cryogenic multipass cell with 93 m optical path length and regulated
at 165 ± 2 K temperature, we recorded a spectrum of the ν6 far-infrared region thanks to the performances of the AILES
Beamline at the SOLEIL french synchrotron facility. Low temperature was used to avoid the presence of the 2ν6 − ν6 hot
band and to reduce the neighboring, stronger ν4 − ν2 difference band. We are thus able to confirm that the small feature
in this region, previously viewed at low-resolution is indeed ν6 . We present its fully resolved spectrum. It appears to be
activated thanks to unidentified faint interactions resulting in the presence of a first-order dipole moment term that induces
unusual selection rules. This spectrum was analyzed thanks to the XTDS software packageb, leading to accurate molecular
spectroscopic parameters that should be useful to model the hot bands of SF6 .
a W.
B. Person, B. J. Krohn, J. Mol. Spectrosc. 98, 229–257 (1983), C. Chappados, G. Birnbaum, J. Mol. Spectrosc. 105, 206–214 (1984).
Wenger, V. Boudon, M. Rotger, M. Sanzharov and J.-P. Champion, J. Mol. Spectrosc., 251 102–113 (2008).
b Ch.
RI09
15 min 4:02
FREQUENCY ANALYSIS OF THE 10 µm REGION OF THE ETHYLENE SPECTRUM USING THE D2h TOP DATA
SYSTEM.
M.-T. BOURGEOIS, M. ROTGER, Groupe de Spectrométrie Moléculaire et Atmosphérique, CNRS UMR
7331, Université de Reims Champagne-Ardenne, Moulin de la Housse, B.P. 1039, Cases 16-17, F-51687 Reims
Cedex, France; M. TUDORIE, J. VANDER AUWERA, Service de Chimie Quantique et Photophysique, C.P.
160/09, Université Libre de Bruxelles, 50, avenue F. D. Roosevelt, B-1050 Brussels, Belgium; V. BOUDON,
Laboratoire Interdisciplinaire Carnot de Bourgogne, CNRS UMR 6303, Université de Bourgogne, 9, Avenue
Alain Savary, BP 47870, F-21078 Dijon Cedex, France.
New high resolution IR spectra of the ν10 /ν7 /ν4 region, lying from 600 cm−1 to 1200 cm−1 have been recorded in
Brussels. They are used simultaneously with a previous spectrum of the ν12 band, also recorded in Brussels, to perform the
analysis of the ν10 /ν7 /ν4 /ν12 region, lying from 600 cm−1 to 1500 cm−1 . Following our work devoted to the ν12 band
considered as isolated, we performed a frequency re-analysis of the ν10 /ν7 /ν4 /ν12 infrared tetrad in the 600 − 1500 cm−1
region, thanks to the tensorial formalism developed in Dijon for X2 Y4 asymmetric-top moleculesa and the XTDS software
packageb. Including the strong Coriolis interaction affecting the upper vibrational levels 101 , 71 , 41 and 121 , a total of
11727 lines have been assigned and fitted as a tetrad with a global root mean square deviation of 0.338 × 10−3 cm−1 .
a W.
Raballand, M. Rotger, V. Boudon and M. Loëte, J. Mol. Spectrosc., 217 239–248 (2003).
Wenger, V. Boudon, M. Rotger, M. Sanzharov and J.-P. Champion, J. Mol. Spectrosc., 251 102–113 (2008).
b Ch.
317
RI10
15 min 4:19
INFRARED ABSORPTION SPECTRUM OF THE SIMPLEST CRIEGEE INTERMEDIATE CH2 OO
YU-TE SU, YU-HSUAN HUANG, HENRYK WITEK, Department of Applied Chemistry and Institute of
Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan; YUAN-PERN LEE, Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu
30010, Taiwan and Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan.
The Criegee intermediates are carbonyl oxides postulated to play key roles in the reactions of ozone with unsaturated hydrocarbons; these reactions constitute an important mechanism for the removal of unsaturated hydrocarbons and for the
production of OH in the atmosphere. Here we report the transient infrared (IR) absorption spectrum of the simplest Criegee
intermediate CH2 OO, produced from CH2 I + O2 in a flow reactor, using a step-scan Fourier-transform spectrometer coupled with a mulitpass absorption cell. CH2 I was produced on photolysis of CH2 I2 with laser light at 248 nm. The five
bands observed near 1435, 1286, 1241, 908, and 848 cm−1 provide definitive identification of this intermediate on comparison of anharmonic vibrational wavenumbers and relative IR intensities predicted using quadratic force field obtained
with the NEVPT2 method implemented in the MOLPRO quantum chemistry package using the CASSCF(8,8) reference
wave function. Observed rotational contours also agree with those simulated based on rotational constants predicted with
the B3LYP method. Observation of the out-of-plane CH2 -wagging (ν8 ) mode near 848 cm−1 with a characteristic c-type
structure showing a prominent Q-branch further supports the assignment of the observed features to a planar CH2 OO. The
observed vibrational frequencies are more consistent with a zwitterion rather than a diradical structure of CH2 OO. The
direct IR detection of CH2 OO should prove useful for kinetic and mechanistic investigations of the Criegee mechanism.
RI11
15 min 4:36
POSSIBLE OBSERVATION OF THE A - A ELECTRONIC TRANSITION OF THE METHYLENE PEROXY
CRIEGEE INTERMEDIATE
3
′
1
′
NEAL D. KLINE and TERRY A. MILLER, Laser Spectroscopy Facility, Department of Chemistry, The Ohio
State University, 120 W. 18th Avenue, Columbus, Ohio 43210; MARC COONS and JOHN HERBERT, Department of Chemistry, The Ohio State University, Columbus, Ohio 43210.
It is possible that we have observed for the first time the transition from the ground 1 A′ state to the low lying 3 A′ state
of the methylene peroxy Criegee intermediate, CH2 O2 , which is otherwise known as carbonyl or formaldehyde oxide.
Criegee intermediates are reactive intermediates that are formed in the ozonolysis of olefins in both liquid and gaseous
phases with the methylene peroxy intermediate being formed specifically from the ozonolysis of ethene. In the atmosphere
Criegee intermediates are formed in reactions that lead to secondary organic aerosols and participate in reactions with SO2
and NO2 . A peroxy-like spectrum was observed in the near-IR using cavity ringdown spectroscopy after photolysis of
a diiodomethane precursor at 248 nm followed by a reaction with O2 . Possible assignment of the spectrum to CH2 O2
is based on a strong analogy between the electronic structure of methylene peroxy and ozone. However experiments and
electronic structure calculations are continuing to positively attribute the spectrum to either CH2 O2 or CH2 IO2 which could
also be formed by this chemistry.
318
RI12
15 min 4:53
UV SPECTRUM AND PHOTOCHEMISTRY OF THE SIMPLEST CRIEGEE INTERMEDIATE CH2 OO
JOSEPH M. BEAMES, FANG LIU, LU LU, and MARSHA I. LESTER, Department of Chemsitry, University
In the troposphere, ozonolysis of ethene as well as other terminal alkenes, such as isoprene, results in formation of the
simplest Criegee intermediate, CH2 OO, which gives rise to many products of atmospheric significance. In the laboratory,
CH2 OO is prepared in a quartz capillary tube reactor using a new synthetic routea based on 248 nm photolysis of CH2 I2
and subsequent reaction with O2 . The CH2 OO and other products undergo supersonic expansion, and are detected using
fixed frequency VUV ionization (118 nm) with mass (m/z=46) and isomer selectivity. Spectroscopic studies of CH2 OO
are carried out by UV laser excitation on the B 1 A′ -X 1 A′ transition prior to photoionization, which results in significant
depletion of the ion signal (approaching 100%) near the peak of a broad absorption profile centered at 335 nm.b The large
depletion and broad absorption are indicative of rapid dissociation, consistent with the repulsive B 1 A′ state potential in
the O-O coordinate that has been computed theoretically. The experimental spectrum is in very good agreement with the
absorption spectrum calculated using the one-dimensional reflection principle. The atmospheric lifetime of CH2 OO due
to solar photolysis at midday is estimated to be ∼ 1 s. These findings provide a UV spectral signature of the strong π ∗ -π
transition associated with the four π electrons on the carbonyl oxide group in CH2 OO. Extensions of this work to methyl
substituted Criegee intermediates reveal similar absorption features arising from the COO π -system .
a O.
b J.
Welz, J. D. Savee, D. L. Osborn, S. S. Vasu, C. J. Percival, D. E. Shallcross, and C. A. Taatjes, Science 335, 204 (2012).
M. Beames, F. Liu, L. Lu, and M. I. Lester, J. Am. Chem. Soc. 134, 20045 (2012).
RI13
15 min 5:10
SPECTROSCOPIC CHARACTERIZATION OF AN ALKYL-SUBSTITUTED CRIEGEE INTERMEDIATE CH3 CHOO
AND ITS OH RADICAL PRODUCTS
JOSEPH M. BEAMES, FANG LIU, LU LU and MARSHA I. LESTER, Department of Chemsitry, University
In the atmosphere, cycloaddition of ozone to the double bond of alkenes produces energized Criegee intermediates, which
undergo subsequent decay processes to yield OH radicals. In this laboratory, a simple alkyl-substituted Criegee intermediate CH3 CHOO is produced by 248 nm photolysis of CH3 CHI2 and subsequent reaction of CH3 CHI with O2 in a quartz
capillary tube reactor, following the same approach utilized for CH2 OO.a The CH3 CHOO intermediate (m/z=60) and other
products are detected following supersonic expansion using 118 nm VUV ionization in a time-of-flight mass spectrometer.
The OH radical products from decomposition of the CH3 CHOO intermediate are also directly detected at m/z=17 using a
new UV+VUV ionization scheme, combining UV excitation on the OH A 2 Σ+ -X 2 Π (1,0) transition with fixed-frequency
VUV at 118 nm,b or alternatively by UV laser-induced fluorescence on the OH A-X transition; OH products are also
observed from CH2 OO. The CH3 CHOO intermediate is characterized by a strong B 1 A′ -X 1 A′ electronic transition, in
which UV excitation near the peak of a broad absorption profile centered at 320 nm results in significant depletion of the
CH3 CHOO photoionization signal. The mechanism proposed for OH generation from energized CH3 CHOO and many
larger Criegee intermediates is a 1,4 H-atom shift to form vinylhydroperoxide species that decay to produce OH. This
reaction scheme provides a non-photolytic source of OH radicals in the atmosphere during night and winter times.
a J.
b J.
M. Beames, F. Liu, L. Lu, and M. I. Lester, J. Am. Chem. Soc. 134, 20045 (2012).
M. Beames, F. Liu, M. I. Lester and C. Murray, J. Chem. Phys. 134, 241102 (2011).
319
RI14
15 min 5:27
RATE CONSTANTS AND DEUTERIUM KINETIC ISOTOPE EFFECTS FOR METHOXY RADICAL REACTING
WITH NO2 AND O2
J. CHAI, H. HU, T. S. DIBBLE, Department of Chemistry, College of Environmental Science and Forestry,
State University of New York, Syracuse, New York 13210; G. S. TYNDALL, J. J. ORLANDO, Atmospheric
Chemistry Division, National Center for Atmospheric Research, Boulder, Colorado 80305.
Alkoxy radicals (RO) are important intermediates in the photooxidation of volatile organic compounds due to their great
impacts on ozone formation and gas-particle partitioning of stable oxidation products. Methoxy radical (CH3 O) is the
prototype for all alkoxy radicals. The absolute rate constants kN O 2 (T) for reaction of CH3 O and CD3 Owith NO2 have
been measured using laser flash photolysis to generate radicals and laser-induced fluorescence for time-resolved detection.
The pressure and temperature dependence for kN O2 have been observed over the range 30-700 Torr and 250-335 K. This
will be the first direct measurement of kN O2 for CH3 O near ambient pressure and the first ever for CD3 O.The relative rate
constants kN O 2 /kO2 (T) have been measured in an environmental chamber with FTIR detection. This combination enables
the first determination of kO2 (T) for CH3 O and CD3 O for T < 298 K. The results will also help validate theoretical
methods for studying alkoxy + O2 reactions, which are challenging for quantum chemistry.
RI15
15 min 5:44
ABSOLUTE VUV PHOTOIONIZATION SPECTRA FOR HCHO, HO2 , AND H2 O2 FROM 10.5-12.0 eV
LEAH G. DODSONa , LINHAN SHEN, NATHAN C. EDDINGSAASb , KANA TAKEMATSU, California
Institute of Technology, Division of Chemistry and Chemical Engineering, Pasadena, CA; JOHN D. SAVEE,
OLIVER WELZ, CRAIG A. TAATJES, DAVID L. OSBORN, Sandia National Lab, Livermore, CA; STANLEY P. SANDER, Jet Propulsion Laboratory, Pasadena, CA; MITCHIO OKUMURA, California Institute of
Technology, Division of Chemistry and Chemical Engineering, Pasadena, CA.
The absolute vacuum ultraviolet (VUV) photoionization spectra of formaldehyde (HCHO), the hydroperoxy radical (HO2 )
and hydrogen peroxide (H2 O2 ) have been measured. The ability to quantify these species is critical for photoionization
mass spectrometry studies of the kinetics of atmospheric and combustion reactions, which require accurate cross sections
over a wide range of ionization energies. Experiments were performed at the Advanced Light Source (ALS) synchrotron
at the Lawrence Berkeley National Laboratory. HCHO, HO2 , and H2 O2 were generated from the oxidation of methanol
which is initiated by pulsed-laser-photolysis of Cl2 in a low pressure flow cell. Sampled gas was ionized by tunable VUV
radiation from the ALS synchrotron and detected by time-resolved multiplexed photoionization mass spectrometry using
the Sandia Multiplexed Chemical Kinetics Reactor.c The photoionization spectra were obtained by scanning the photon
energy from 10.5 to 12.0 eV. Absolute cross sections were determined relative to methanol from measurements of the
depletion of precursors and kinetic modeling of the initial chemistry (< 10 ms). The absolute photoionization spectrum of
HCHO and the relative photoionization spectra of HO2 and H2 O2 are in good agreement with previous work.d,e
a Support
from the EPA STAR fellowship and NSF grant CHE-095749 are gratefully acknowledged
address: Rochester Institute of Technology, Rochester, NY
c D. L. Osborn, P. Zou, H. Johnson, C. C. Hayden, C. A. Taatjes, V. D. Knyazev, S. W. North, D. S. Peterka, M. Ahmed, S. R. Leone. Rev. Sci. Inst.
2008, 79, 104103.
d G. Cooper, J. E. Anderson, C. E. Brion. Chem. Phys. 1996, 209, 61.
e M. Litorja, B. J. Ruscic. Electron Spectrosc. Relat. Phenom. 1998, 97, 131.
b Present
320
RI16
LABORATORY INVESTIGATION OF THE AIRGLOW BANDS
15 min 6:01
BRIAN DROUIN, SHANSHAN YU, TIMOTHY J. CRAWFORD, CHARLES E. MILLER, Jet Propulsion
Laboratory, California Institute of Technology, 4800 Oak Grove Dr., Pasadena, CA 91109; JENG-HWA YEE,
Applied Physics Laboratory, The Johns Hopkins University, 111000, Johns Hopkins Rd, Laurel, MD 207236099.
We report the first high spectral resolution laboratory measurements of oxygen A-band night glow simulated using a static
discharge cell. Our static discharge system reproduces the conditions of the mesospheric oxygen night glow - suggesting
O(1 D) + O2 as the primary source of the emission. Additionally, use of the static cell has enabled us to collect spectra
for rare molecular oxygen isotopologues using isotopically enriched samples. The (0,0), (0,1), and (1,1) b − Xvibrational
bands were observed with a Bruker 125 HR for all six isotopologues. The (1,2) and (2,2) bands were observed also for
the main isotopologue. The frequencies of the observed (0,1) transitions resolved discrepancies in Raman data for (16-17,
17-17, and 17-18), enabling us to improve the vibrational parameterization of the ground electronic state in the global fit
of Yu et al.a Rotationally resolved intensities were determined for the (0,0), (0,1) and (1,1) bands. The experimental band
intensity ratios I(0,0)/I(0,1) = 13.6 and I(0,0)/I(1,1) = 60 are in excellent agreement with the recent mesospheric remote
sensing data.
a S.
Yu, C.E. Miller, B.J. Drouin, H.S.P. Müller, J. Chem. Phys. 136, 024304, 2012
321
RJ. INFRARED/RAMAN
Chair: LAURA MCCUNN, Marshall University, Huntington, WV
RJ01
15 min 1:30
EXPERIMENTAL FT-IR, DISPERSIVE RAMAN AND THEORETICAL DFT CALCULATIONS ON CU(II) CHLORIDE COMPLEX OF P-TOLUIDINE
TAYYIBE BARDAKCI, MUSTAFA KUMRU, Department of Physics, Faculty of Arts and Sciences, Fatih
University, 34500 Buyukcekmece, Istanbul, Turkey.
In this study Cu(p-tol)2Cl2 (p-tol: p-toluidine) is prepared and characterized by elemental analysis, FT-IR, FT-FIR, and
dispersive Raman spectral analysis. The molecular geometry and vibrational modes of p-tol and Cu(p-tol)2Cl2 are calculated using DFT- BVP86 and DFT-B3LYP methods with 6-311G+(d,p) basis set. The optimized geometries and calculated
vibrational frequencies have been evaluated via comparison with experimental values, and the normal modes were assigned
on the basis of the percent potential energy distribution (PED). The coordination effects on vibrational frequencies of p-tol
are discussed by comparing the spectra of free p-tol and its Cu (II) chloride complex. A good agreement between calculated
and experimental data is observed.
Keywords: IR and Raman spectra; DFT; p-toluidine; Copper (II) chloride complex
RJ02
15 min 1:47
INFRARED SPECTROSCOPY OF PHENOL-TRIETHYLSILANE DIHYDROGEN-BONDED CLUSTER
HARUKI ISHIKAWA, TAKAYUKI KAWASAKI, Department of Chemistry, School of Science, Kitasato University, Minami-ku, Sagamihara 252-0373, Japan.
Dihydrogen bond is a hydrogen bond between oppositely charged two hydrogen atoms, X-H· · · H-Y, where X = O, N
and Y = B, metal atoms, for example. In 2005, Ishikawa and coworkers reported the observation of the dihydrogen-bond
system involving Si-H group as the proton acceptora. They carried out infrared (IR) spectroscopy of phenol(PhOH)Diethylmethylsilane(DEMS) clusters. All of the three isomers of PhOH-DEMS 1:1 clusters observed exhibit a small redshift of ν̃OH of the PhOH moiety in the cluster compared with that of bare PhOH. The largest shift is −29 cm−1 . The small
red-shift is considered to be the result of the competition between the O-H· · · H-Si dihydrogen-bond and the dispersion
interaction of alkyl group of DEMS with phenyl ring. It means that the strength of the O-H· · · H-Si dihydrogen-bond is
comparable to the dispersion force.
In the present study, we have performed fluorescence excitation (FE) and IR spectroscopies of phenol-triethylsilane(TES)
to widen the knowledge of the dihydrogen bond. Similar to the case of PhOH-DEMS system, the electronic origin bands
of three PhOH-TES isomers appear in the vicinity of that of PhOH monomer in the FE spectrum. In the present study, we
have found an origin band of another PhOH-TES isomer showing a red-shift of −120 cm−1 . The shift of ν̃OH of this cluster
is found to be −78 cm−1 . This value is much larger than those of the other PhOH-TES 1:1 clusters. It is expected that the
spatial overlap of between the TES and the phenyl ring in this cluster is small so that the contribution of the O-H· · · H-Si
dihydrogen-bond becomes larger than the other isomers. We have performed density-functional-theory (DFT) calculation
of the PhOH-TES clusters using M05-2X functional. The result of the DFT calculation supported the cluster structure and
the large red-shift of ν̃OH of the newly found isomer of PhOH-TES.
a H.
Ishikawa, A. Saito, M. Sugiyama, N. Mikami, J. Chem. Phys. 123, 224309 (2005).
322
RJ03
10 min 2:04
A NEW, LOW TEMPERATURE LONG PATH CELL FOR MID-IR to THz SPECTROSCOPY WITH SYNCHROTRON
RADIATION AT SOLEIL
F. KWABIA TCHANA, F. WILLAERT, X. LANDSHEERE, J.M. FLAUD, Laboratoire Interuniversitaire
des Systémes Atmosphériques (LISA), UMR CNRS 7583, Université Paris-Est Créteil (UPEC) et Université
Paris-Diderot (UPD), 61 Avenue du Général de Gaulle, 94010 Créteil Cedex, France; L. LAGO, M. CHAPUIS, P. ROY„ Synchrotron SOLEIL, L’Orme des Merisiers Saint-Aubin, 91192 Gif-sur-Yvette, France;
L. MANCERON, Laboratoire LADIR, UMR7075 CNRS, Université Pierre et Marie Curie, 75252 Paris Cedex,
France.
In this talk we will present the details and performances of a new cell, specially designed for accurate spectroscopic
measurements in the 80 to 400K temperature range with variable path lengths from 3 to more than 140m as well as to
accommodate the specific requirements of high resolution measurements in the mid-IR, as well as on the Far-Infrared
(FIR) AILES beamline at SOLEIL. The spectral coverage at these temperatures ranges from the visible to less than 10
cm−1 , thanks to the use of diamond windows. The design of the cryostatic and vacuum set-up allows vibration-free
operation. The equipment provides for temperature homogeneity and pressure control to better than 2 percent over the
100 to 400K and 0.1 to 1000 mbar ranges. Remote-controlled opto-mechanical systems enable in situ readjustements as
well as changes of the optical path length within half an hour, in order to optimize measurement time in an open user
facility. The design and performance of the equipment will be briefly presented and illustrated on spectroscopic examples.
This new instrument opens up the way for many experiments in the field of high-resolution gas-phase IR spectroscopy, in
particular in quantitative spectroscopy for atmospheric applications: measurements of absorption line parameters (absolute
intensities and pressure-induced widths) using Fourier transform spectroscopy.
RJ04
10 min 2:16
SYNCHROTRON BASED HIGH RESOLUTION FAR-IR SPECTROSCOPY OF 1,1-DICHLOROETHYLENE
REBECCA A. PEEBLES, LENA F. ELMUTI, and SEAN A. PEEBLES, Department of Chemistry, Eastern
Illinois University, 600 Lincoln Ave., Charleston, IL 61920; DANIEL A. OBENCHAIN, Department of Chemistry, Wesleyan University, 52 Lawn Avenue, Middletown, CT 06459-0180.
Six vibrational bands of the 35 Cl2 C=CH2 isotopologue of 1,1-dichloroethylene have been recorded in the 350 – 1150 cm−1
range using the 0.00096 cm−1 resolution far-infrared beamline of the Canadian Light Source synchrotron facility. Results
from the analysis of one a-type (ν9 = 796.01904(8) cm−1 , CCl asymmetric stretch) and one c-type (ν11 = 868.488626(26)
cm−1 , CH2 flap) band will be presented. Over 6000 transitions have now been fitted for these two bands, with ground state
rotational and centrifugal distortion constants fixed to values determined by rotational spectroscopy,a while the upper state
constants have been varied. Anharmonic frequency calculations at the MP2/6-311++G(2d,2p) level were instrumental in
assigning the dense spectra. Assignment of additional bands around 603 cm−1 (b-type, CCl symmetric stretch, ν4 ) and 456
cm−1 (c-type, CCl2 flap, ν12 ), as well as attempts at assigning the mixed 35 Cl37 Cl isotopologue spectra for ν9 and ν11 , are
in progress.
a Z.
Kisiel, L. Pszczółkowski, Z. Naturforsch, 50a, (1995), 347-351.
RJ05
15 min 2:28
SYNCHROTRON-BASED STUDY OF THE FAR IR SPECTRUM OF SILACYCLOBUTANE: THE ν29 AND ν30
BANDS
ZIQIU CHEN, CODY W. VAN DIJK, SAMANTHA HARDER AND JENNIFER VAN WIJNGAARDEN,
Department of Chemistry, University of Manitoba, Winnipeg MB R3T 2N2 Canada.
Rotationally-resolved vibrational spectra of the four-membered ring silacyclobutane (c-C3 H8 Si) from 100-1000 cm−1 have
been collected (resolution: 0.00096 cm−1 ) using the far infrared beamline at the Canadian Light Source synchrotron. The
two lowest frequency vibrational bands recorded correspond to motions that are best described as ring puckering (ν30 ) at
158 cm−1 and SiH2 rocking (ν29 ) at 410 cm−1 . Close examination of the two bands reveals that each is split into two
tunneling components due to ring inversion. The assignment and analysis of the dense rovibrational patterns in these two
regions will be detailed. Ongoing work involving the assignment of higher frequency bands will also be discussed.
323
RJ06
15 min 2:45
GAS PHASE VIBRATIONAL SPECTROSCOPY OF WEAKLY VOLATIL SAFE TAGGANTS USING A SYNCHROTRON SOURCE
ARNAUD CUISSET, FRANCIS HINDLE, GAEL MOURET, Laboratoire de Physico-Chimie de
l’Atmosphère, 189A Ave. Maurice Schumann, 59140 Dunkerque, France; SEBASTIEN GRUET, OLIVIER
PIRALI, PASCALE ROY, Ligne AILES, synchrotron SOLEIL, L’Orme des Merisiers, Saint Aubin, BP 48,
91192 Gif-sur-Yvette, France..
The high performances of the AILES beamline of SOLEIL allow to study at medium resolution (0.5 cm−1 ) the gas phase
THz vibrational spectra of weakly volatil compounds. Between 2008 and 2010 we recorded and analyzed the THz/Far-IR
spectra of phosphorous based nerve agents thanks to sufficient vapour pressures from liquid samples at room temperaturea b .
Recently, we extended these experiments towards the vibrational spectroscopy of vapour pressures from solid samples. This
project is quite challenging since we target lower volatile compounds, and so requires very high sensitive spectrometers.
Moreover a specially designed heated multipass-cell have been developped for the gas phase study of very weak vapor
pressures. Thanks to skills acquired during initial studies and recent experiments performed on AILES with solid PAHsc ,
we have recorded and assigned the gas phase vibrational fingerprints from the THz to the NIR spectral domain (10-4000
cm-1) of a set of targeted nitro-derivatives. The study was focused onto the para, ortho-mononitrotoluene (p-NT, o-NT),
the 1,4 Dinitrobenzene (1,4 DNB), the 2,3-dimethyl-2,3-dinitrobutane (DMNB), and 2,4 and 2,6-dinitrotoluene (2,4-2,6
DNT), which are safe taggants widely used for the detection of commercial explosives. These taggants are usually added to
plastic explosives in order to facilitate their vapour detection. Therefore, there is a continuous interest for their detection and
identification in realistic conditions via optical methods. A first step consists in the recording of their gas phase vibrational
spectra. These expected spectra focused onto molecules involved into defence and security domains are not yet available
to date and will be very useful for the scientific community. This work is supported by the contract ANR-11-ASTR-035-01.
a A.
Cuisset, G. Mouret, O. Pirali, P. Roy, F. Cazier, H. Nouali, J. Demaison, J. Phys. Chem. B, 2008, 112:, 12516-12525
Smirnova, A. Cuisset, R. Bocquet, F. Hindle, G. Mouret, O. Pirali, P. Roy, J. Phys. Chem. B, 2010, 114: 16936-16947.
c M. A. Martin-Drumel, O. Pirali, Y. Loquais, C. Falvo, P. Brechignac Chem. Phys. Lett., 2013, 557:, 53-58
b I.
RJ07
15 min 3:02
SYNCHROTRON BASED FOURIER TRANSFORM FAR-INFRARED SPECTROSCOPY OF CH3NO2
SYLVESTRE TWAGIRAYEZU, BRANT E. BILLINGHURST AND TIM MAY , Canadian Light Source
Inc., University of Saskatchewan, 44 Innovation Blvd, Saskatoon, SK S7N 2V3; MAHESH B. DAWADI,
DAVID S. PERRY, Department of Chemistry, The University of Akron, Akron OH 44325.
As a slightly asymmetric top molecule (κ = 0.25) with both a free internal rotor and a methyl group, CH3 NO2 is a
benchmark system for studies of torsional motion in a 6-fold potential and of the coupling between a large amplitude
vibration and other small-amplitude vibrations. For this purpose, rotationally resolved infrared spectra of CH3 NO2 , have
been recorded using the Far-Infrared beamline at the Canadian Light Source, which is equipped with a high resolution
Bruker IFS 125HR spectrometer. The observed infrared spectra, in the range 550-1000cm−1, are the average of 300
interferometer scans collected at a nominal resolution of 0.00096cm−1. Two a-type bands, centered at 657.08cm−1for NO
symmetric bend and at 917.99cm−1for CN-stretch, have been measured. The initial analysis of a number of torsional states
is currently being carried out and the progress will be reported in this talk.
Intermission
324
RJ08
15 min 3:40
ISOLATION AND CHARACTERIZATION OF FORMATE/NI(CYCLAM)
VIBRATIONAL PREDISSOCIATION
2+
COMPLEXES WITH CRYOGENIC ION
ARRON B. WOLK, JOSEPH A. FOURNIER , CONRAD T. WOLKE, and MARK A. JOHNSON, DEPARTMENT OF CHEMISTRY, YALE UNIVERSITY, NEW HAVEN, CT 06520.
Transition metal-based organometallic catalysts are a promising means of converting CO2 to transportable fuels.
Ni(cyclam)2+(cyclam = 1,4,8,11-tetraazacyclotetradecane), a NiII complex ligated by four nitrogen centers, has shown
promise as a catalyst selective for CO2 reduction in aqueous solutions. The cyclam ligand has four NH hydrogen bond
donors that can adopt five conformations, each offering distinct binding motifs for coordination of CO2 close to the metal
center. To probe the ligand conformation and the role of hydrogen bonding in adduct binding, we extract Ni(cyclam)2+
complexes with the formate anion and some of its analogs from solution using electrospray ionization, and characterize
their structures using cryogenic ion vibrational predissociation spectroscopy. Using the signature vibrational features of
the embedded carboxylate anion and the NH groups as reporters, we compare the binding motifs of oxalate, benzoate, and
formate anions to the Ni(cyclam)2+ framework. Finally, we comment on possible routes to generate the singly charged
Ni(cyclam)+ complex, a key intermediate that has been invoked in the catalytic CO2 reduction cycle, but has never been
isolated through ion processing techniques.
RJ09
15 min 3:57
CHARACTERIZATION OF STRUCTURAL MOTIFS FOR CO2 ACCOMMODATION BY IONIC SPECIES RELEVANT TO PHOTOELECTROCATALYSIS USING CRYOGENIC VIBRATIONAL PREDISSOCIATION SPECTROSCOPY
JOSEPH A. FOURNIER, CHRISTOPHER J. JOHNSON, CONRAD T. WOLKE, ARRON B. WOLK,
CHRISTOPHER M. LEAVITT, KRISTEN J. BREEN, and MARK A. JOHNSON, DEPARTMENT OF
CHEMISTRY, YALE UNIVERSITY, NEW HAVEN, CT 06520.
Two aspects of catalytic CO2 conversion to transportable fuels involve understanding the local interactions between CO2
and the solvent mediating the reduction and the coordination of CO2 onto the organometallic framework that executes the
chemical transformation. To address why ionic liquids are emerging as the solvents of choice for the catalysis, we first
explore how CO2 attaches to two archetypal ionic liquid components: imidazole (Im) and acetate (Ac− ). Im was seeded
in a CO2 pulsed free jet expansion forming Im(CO2 − )(CO2 )m (m=1-2) clusters. Previous studies with pyridine revealed
C-N bond formation between CO2 − and pyridine with m=5 or 7, evidenced by the observation of a C-N stretch in the
vibrational spectra. No such C-N bond formation is observed with Im; the CO2 − appears to be hydrogen bonded to the Im
N-H in an ion-molecule complex. Attachment to Ac− was studied by predissociation of the Ac− (CO2 )m (m=1-4) clusters
and, for m=1-3, a single peak assigned to the CO2 asymmetric stretch is observed near that of bare CO2 , suggesting that the
CO2 molecules are weakly bound adducts. However, the combination bands 2ν2 + ν3 and ν1 + ν3 in the 3600 − 3750cm−1
region reveal two distinct binding sites: a neutral site and a red-shifted, more perturbed site. For m=4, a red-shifted CO2
asymmetric stretch is observed, perhaps indicating the beginning of solvent mediated activation of a CO2 adduct.
Finally, the CO2 reduction catalyst Ni(cyclam)2+ has been investigated using an electrospray ionization source coupled
to a cryogenically cooled ion trap. By adding CO2 to the He buffer gas used to collisionally cool the ions in the trap, we
have been able to condense up to five CO2 molecules onto Ni(cyclam)2+ at a trap temperature of 100K. The cryogenic ion
vibrational predissociation (CIVP) spectra show the CO2 molecules to be acting as neutral adducts. We are now working
to develop a method to generate and isolate the reactive Ni(cyclam)+ and capture the bound-CO2 intermediate.
325
RJ10
Post-deadline Abstract - Original Abstract Withdrawn
15 min 4:14
THZ SPECTROSCOPY AND DFT MODELING OF INTERMOLECULAR VIBRATIONS IN HYDROPHOBIC
AMINO ACIDS
MICHAEL R. C. WILLIAMS, DANIEL J. ASCHAFFENBURG, CHARLES A. SCHMUTTENMAER, Yale
University, Department of Chemistry, P.O. Box 208107, 225 Prospect St., New Haven, CT 06520-8107, USA..
Vibrations that involve intermolecular displacements occur in molecular crystals at frequencies in the 0.5-5 THz range
(∼15-165 cm−1 ), and these motions are direct indicators of the interaction potential between the molecules. The
intermolecular potential energy surface of crystalline hydrophobic amino acids is inherently interesting simply because of
the wide variety of forces (electrostatic, dipole-dipole, hydrogen-bonding, van der Waals) that are present. Furthermore,
an understanding of these particular interactions is immediately relevant to important topics like protein conformation and
pharmaceutical polymorphism.
We measured the low-frequency absorption spectra of several polycrystalline hydrophobic amino acids using THz timedomain spectroscopy, and in addition we carried out DFT calculations using periodic boundary conditions and an exchangecorrelation functional that accounts for van der Waals dispersion forces. We chose to investigate a series of similar amino
acids with closely analogous unit cells (leucine, isoleucine, and allo-isoleucine, in racemic or pseudo-racemic mixtures).
This allows us to consider trends in the vibrational spectra as a function of small changes in molecular arrangement and/or
crystal geometry. In this way, we gain confidence that peak assignments are not based on serendipitous similarities between
calculated and observed features.
RJ11
15 min 4:31
STRUCTURES AND THE HYDROGEN BONDING ABILITIES OF ESTROGENS STUDIED BY SUPERSONIC
JET/LASER SPECTROSCOPY
FUMIYA MORISHIMA, YOSHIYA INOKUCHI and TAKAYUKI EBATA, Graduate School of Science, Hiroshima University 1-3-1, Kagamiyama, Higashi-Hiroshima 739-8526, JAPAN.
Estrone, estradiol, estriol are known as endogenous estrogen which have the same steroidal frame with different substituent,
leading to difference of physiological activity upon the formation of hydrogen bond with estrogen receptor. In the present
study, structures of estrogens and their hydrated clusters in a supersonic jet have been studied by various laser spectroscopic
techniques and density functional theory calculation to study how the difference of substituents affects their hydrogen
bonding ability. Infrared spectra in the OH stretching region indicate a formation of intramolecular hydrogen-bond in
estriol, which may lead to weaker physiological activity among the three estrogens. We also measured electronic and
infrared spectra of 1:1 hydrated clusters of estrogen. The results show a switch of stable hydration site from the phenolic
OH group to the five member ring by substituting one more OH group.
326
RJ12
15 min 4:48
DEUTERATION EFFECT ON THE NH/ND STRETCH BAND OF THE JET-COOLED 7-AZAINDOLE AND ITS TAUTOMERIC DIMERS: RELATION TO THE GROUND-STATE DOUBLE PROTON-TRANSFER REACTION
HARUKI ISHIKAWA, Department of Chemistry, School of Science, Kitasato University,
Minami-ku, Sagamihara 252-0373, Japan; TAKUMI NAKANO, TSUKIKO TAKASHIMA, HIROKI YABUGUCHI, and KIYOKAZU FUKE, Department of Chemistry, Graduate School of Scinec,
Kobe University, Nada-ku, Kobe 657-8501, Japan.
In order to investigate the deuteration effect on the vibrational dynamics of the NH and/or ND stretch excited levels of the 7azaindole (7-AI) normal dimer and its tautomeric dimer, we have carried out infrared spectroscopy of three isotopic species
for each dimers; undeuterated one (NH-NH) and one or two hydrogen atom(s) of the NH groups is deuterated ones (NH-ND
and ND-ND, respectively). It is found that the ND stretch band profiles of the NH-ND and ND-ND tautomeric dimers are
very similar with each other. This result is very distinct from the result of the comparison of the NH stretch band profiles of
the NH-NH and NH-ND dimers in our previous studya . For a further discussion, we have examined the deuteration effect
in the case of the 7-AI normal dimer. It is found that the NH stretch band profiles of the NH-NH and the NH-ND dimers
and also the ND stretch band profiles of the NH-ND and the ND-ND dimers exhibit similar patterns, respectively. These
facts indicates that the vibrational relaxation from the NH/ND stretch level of the normal dimer basically proceed within a
monomer unit. The large deuteration effect of the NH stretch band profile observed previously is found to be characteristic
of the tautomeric dimer. This behavior is related to a large anharmonicity of the potential energy surface originating from
an existence of the double-proton transfer reaction barrier.
a H.
Ishikawa, H. Yabuguchi, Y. Yamada, A. Fujihara, K. Fuke, J. Phys. Chem. A 114, 3199 (2010).
RJ13
10 min 5:05
SOLVENT EFFECTS ON IR MODES OF (R)-3-METHYLCYCLOPENTANONE CONFORMERS: A COMPUTATIONAL INVESTIGATION
WATHEQ AL-BASHEER, Physics Department, King Fahd University of Petroleum and Minerals, Dhahran
31261 Saudi Arabia.
Density Functional Theory (DFT) calculations of infrared spectra for the optimized geometries of R-(+)-3methylcyclopentanone (R3MCP) equatorial-methyl and axial-methyl conformers were performed in 11 common solvents
of wide polarity range, in the framework of polarizable continuum model (PCM). DFT correlation function type B3LYP
using a powerful basis set (aug-cc-pVDZ) yielded different linear correlation between solvent polarity and R3MCP equatorial and axial conformers IR modes frequencies, intensities, and enthalpies (W. Al-Basheer, J. Sol. Chem. 41, 1495-1506
(2012)). DFT calculations of the R3MCP equatorial and axial conformer dipole moment components in 3D were also
carried out and found to have a linear correlation with solvent polarity (W. Al-Basheer et al, J. Phys. Chem. A 111(12),
2293-2298 (2007)). An observed trend for a Hypsochromic (blue) shift in the equatorial conformer IR frequencies, in
comparison to Bathochromic (red) shift for the axial-methyl conformer IR modes as a function of solvent polarity increase.
RJ14
CHIRAL RECOGNITION IN NEUTRAL AND IONIC MOLECULAR COMPLEXES
15 min 5:17
ANANYA SEN, AUDE BOUCHET, VALERIA LEPERE, KATIA LE BARBU-DEBUS, and ANNE
ZEHNACKER-RENTIEN, CNRS, Institut des Sciences Moléculaires d’Orsay (ISMO), UMR 8214, Orsay
F-91405, and Univ. Paris-Sud, Orsay F-91405, France.
The behaviour of chiral molecules in the gas phase have been studied. The two pseudoenantiomers of Quinine, have been
put intact in the gas phase using laser ablation and characterized using different spectroscopic techniques such as REMPI,
LIF, IR-UV double resonance. VCD measurements have been performed in solution. From this comparative study one can
conclude that the pseudoenantiomers behave differently both in gas phase and in solutiona .
a Ananya Sen, Aude Bouchet, Valeria Lepère, Katia Le Barbu-Debus, D. Scuderi, F. Piuzzi, and A. Zehnacker-Rentien, J. Phys. Chem. A, 2012, 116
(32), pp 8334-8344
327
RK. MICROWAVE
Chair: SUSANNA WIDICUS WEAVER, Emory University, Atlanta, GA
RK01
10 min 1:30
SPECTROSCOPY OF THE GROUND, FIRST AND SECOND EXCITED TORSIONAL STATES OF ACETALDEHYDE FROM 0.05 TO 1.6 THz.
VADIM V. ILYUSHINa , IVAN SMIRNOV, EUGENE A. ALEKSEEV, Institute of Radio Astronomy of NASU,
Chervonopraporna 4, 61002 Kharkov, Ukraine; LAURENT MARGULÈSb , ROMAN A. MOTIYENKO, Laboratoire de Physique des Lasers, Atomes et Molècules, UMR 8523 CNRS-Universitè Lille 1, Bâtiment P5,
F-59655 Villeneuve d’Ascq Cedex, France; BRIAN DROUIN, Jet Propulsion Laboratory, California Institute
of Technology, 4800 Oak Grove Drive, Pasadena, CA 91109-8099, USA.
A new global study of the acetaldehyde (CH3 CHO) spectrum is reported. The new measurements cover the frequency
range from 49 GHz to 1.6 THz and have been carried out using three different spectrometers in IRA NASU (Ukraine),
PhLAM Lille (France), and JPL (USA). The rotational transitions belonging to the three lowest torsional states, as well as
previously published data on the FIR torsional bands, of the molecule have been analyzed using the rho-axis-method. The
dataset consisting of more than 19700 line frequencies and including rotational transitions with J up to 66 and Ka up to 22
was fit using a model consisting of 117 parameters and weighted root-mean-square deviation of 0.71 has been achieved.
Details of this new study and problems encountered in analysis of the second torsional state will be discussed.
a Part
b This
of this work was done within the Ukrainian-French CNRS-PICS 6051 project.
work was supported by the CNES and the Action sur Projets de l’INSU, PCMI.
RK02
15 min 1:42
A SEMIEXPERIMENTAL EQUILIBRIUM STRUCTURE OF cis-HEXATRIENE FROM MICROWAVE SPECTROSCOPY
NORMAN C. CRAIG, YIHUI CHEN, HANNAH A. FUSON, HENGFENG TIAN, and HERMAN VAN BESIEN, Department of Chemistry and Biochemistry, Oberlin College, Oberlin, Ohio 44074; H. D. RUDOLPH,
Department of Chemistry, University of Ulm, D-89069 Ulm, Germany; JEAN DEMAISON, Laboratoire de
Physique des Lasers, Atomes et Molécules, Université de Lille I, 59655 Villeneuve d’Ascq Cedex, France.
Ground state rotational constants for a full set of carbon and deuterium isotopologues of cis-hexatriene, which has a dipole
moment of only 0.05 D, have been determined by MW spectroscopy.ab Ground state rotational constants were converted
into equilibrium rotational constants with spectroscopic alphas computed from force constants found with an MP2/ccpVTZ model. Corrections for electronic contributions were applied. Despite the availability of a full set of rotational
constants for a suite of isotopologues, an accurate structure was not accessible. The mixed estimation method, in which
high-quality bond parameters computed by quantum chemistry with appropriate uncertainties were fit simultaneously with
the moments of inertia, was applied. A structure good to 0.001 Å was the result. The structural parameters reflect an
increase in pi-electron delocalization compared to butadiene.
a R.
b N.
press.
D. Suenram, B. H. Pate, A. Lesarri, J. L. Neill, S. Shipman, R. A. Holmes, M. C. Leyden, N. C. Craig J. Phys. Chem. A 113, 1864-1868 (2009).
C. Craig, Y. Chen, H. A. Fuson, H. Tian, H. van Besien, A. R. Conrad, M. J. Tubergen, H. D. Rudolph, J. Demaison, J. Phys. Chem. A 117, in
328
RK03
15 min 1:59
ANALYSIS OF THE ROTATIONAL STRUCTURE IN THE HIGH-RESOLUTION INFRARED SPECTRA OF cis, cisAND trans, trans-1,4-DIFLUOROBUTADIENE-1-d1 AND trans, trans-1,4-DIFLUOROBUTADIENE-1,4-d2
NORMAN C. CRAIG, YIHUI CHEN, YUHUA LU, CHRISTOPHER F. NEESE, and DEACON J. NEMCHICK, Department of Chemistry and Biochemistry, Oberlin College, Oberlin, OH 44074; THOMAS A.
BLAKE, Pacific Northwest National Laboratory, Richland, WA 99352.
Samples of cis,cis- and trans,trans-1,4-difluorobutadiene-1-d1 (DFBD) and trans,trans-DFBD-1,4-d2 have been synthesized and investigated with high-resolution (0.0015 cm−1 ) infrared spectroscopy. For the first two species the rotational
structure in more than one band has been analyzed. For the 1,4-d2 species the spectrum of only one C-type band was
available in an isotopic mixture. Ground state rotational constants are reported for all three molecules. It is proposed
that quartic centrifugal distortion constants computed with a B3LYP/cc-pVTZ model can be used to assess the quality of
observed rotational constants. The favorable comparison of predicted and observed ground state rotational constants for all
four 13 C species of cis,trans-DFBD, which is MW active,a demonstrates that the ground state rotational constants for the
13
C species of the cis,cis and trans,trans isomers can be successfully predicted with high accuracy. Rotational constants
for a full set of isotopologues will be used to determine accurate semiexperimental equilibrium structures of the cis,cis and
trans,trans species of DFBD.
a N.
C. Craig, C. M. Oertel, D. C. Oertel, M. J. Tubergen, R. J. Lavrich, A. M Chaka J. Phys. Chem. A 106, 4230-4235 (2002).
RK04
THE DELICATE BALANCE OF HYDROGEN BOND FORCES IN D-THREONINOL
10 min 2:16
DI ZHANG, VANESA VAQUERO VARA, BRIAN C. DIAN and TIMOTHY S. ZWIER, Department of
Chemistry, Purdue University, West Lafayette, IN 47907; DAVID W. PRATT, Department of Chemistry, University of Vermont, Burlington VT 05405.
The molecule of D-threoninol has been studied using CP-FTMW spectroscopy. Despite the small size of this molecule,
a great variety of conformations have been observed in the molecular expansion. With 2 OH groups and one NH2 group,
many possibilities for hydrogen bonding are anticipated. The multiple ways they can interact with each other make the
analysis of its rotational spectrum challenging and only through an exhaustive conformational search and the comparison
with the experimental rotational parameters and line strengths are we able to understand the complex nature of these
interactions. In the 7 conformations already assigned, evidences for hydrogen bonded cycles and chains are revealed with
dipole moment very sensitive to the configuration of the hydrogen bond.
RK05
WAVEGUIDE CHIRPED-PULSE
ETHOXYETHANOL
FOURIER
TRANSFORM
MICROWAVE
10 min 2:28
SPECTROSCOPY OF 2-
MARIA A. PHILLIPS and STEVEN T. SHIPMAN, Division of Natural Sciences, New College of Florida,
Sarasota, FL 34243.
The pure rotational spectrum of 2-ethoxyethanol was recorded from 8.7 to 26.5 GHz at 250 K with a waveguide chirpedpulse Fourier transform microwave spectrometer. The full spectrum contains contributions from multiple vibrational states.
Preliminary assignments have been made with a combination of ab initio calculations and an automated spectral fitting
program that accelerates the initial fitting process.
329
RK06
10 min 2:40
WAVEGUIDE CHIRPED-PULSE FOURIER TRANSFORM MICROWAVE SPECTROSCOPY OF 1-PROPANETHIOL
BRITTANY P. GORDON and STEVEN T. SHIPMAN, Division of Natural Sciences, New College of Florida,
Sarasota, FL 34243.
The rotational spectrum of 1-propanethiol was measured from 8.7 to 26.5 GHz at 250 K with a waveguide chirped-pulse
Fourier transform microwave spectrometer. This thiol has a dense spectrum containing contributions from multiple conformers, excited vibrational states, and singly-substituted isotopomers (34 S and 13 C) in natural abundance. Further, the
spectrum shows complications due to the presence of internal rotation. Despite this complexity, some progress has been
made, and preliminary work on this molecule will be presented.
RK07
15 min 2:52
ENERGY TRANSFER COLLISIONAL PROCESS INVOLVING HETEROMOLECULAR COLLISIONS BETWEEN
METHYL FLUORIDE AND N2 , Ar, He, CO2 , AND AIR
DANE J. PHILLIPS, IERUS Technologies, 2904 Westcorp Blvd Ste 210, Huntsville, AL 35805;
HENRY O. EVERITT, Army Aviation and Missile RD&E Center, Redstone Arsenal, AL 35898.
Time resolved IR/THz double resonance (DR) spectroscopy has been performed with a Q-switched CO2 laser and heterodyne THz detection. The rate constants associated with allowed rotational- and vibrational-state changing collisions
of CH3 F with N2 , Ar, He, CO2 , and air are measured by monitoring the temporal evolution of the absorption strength
for numerous rotational transitions as a function of pressure. Collision partner dependent energy transfer processes are
studied and compared with homomolecular collisions. Energy transfer maps and associated collisional cross sections will
be presented for each collision partner.
RK08
MILLIMETER WAVE TUNNELING-ROTATIONAL SPECTRUM OF PHENOL
15 min 3:09
L. KOLESNIKOVÁ, A. M. DALY, J. L. ALONSO, Grupo de Espectroscopía Molecular (GEM), Edificio
47011 Valladolid, Spain; B. TERCERO, J. CERNICHARO, Departamento de Astrofísica, Centro de Astrobiología CAB, CSIC-INTA, Ctra. de Torrejón a Ajalvir km 4, 28850 Madrid, Spain.
The millimeter wave spectra of phenol in the vibrational ground state and the first excited states of the bending and torsion
vibrational modes have been studied in the frequency regions of 140 – 170 GHz and 280 – 360 GHz. The internal rotation
of the hydroxyl group is responsible for the observed tunneling splitting into two substates (vt , vb )+ and (vt , vb )− and
more than 3500 distinct tunneling-rotational b R- and b Q-type transitions between them were measured and analyzed.
Furthermore, accidental near degeneracies of the (+) and (−) energy levels were observed in case of the ground state and
the vb = 1 excited state and the analysis using a two-state effective Hamiltonian including tunneling-rotational Coriolis
terms was performed. The spectroscopic constants for the first excited states of the bending and the torsion vibrational
modes have been determined for the first time. The analysis of the microwave data provided very precise values of the
spectroscopic constants necessary for the astrophysical search of phenol. We report a tentative detection for this molecule
in the IRAM 30m line survey of Orion KL.
Intermission
330
RK09
ROTATIONAL SPECTROSCOPY UNVEILS ELEVEN CONFORMERS OF ADRENALINE
15 min 3:40
C. CABEZAS, V. CORTIJO, S. MATA, J. C. LÓPEZ, J. L. ALONSO, Grupo de Espectroscopía Molecular
Recent improvements in our LA-MB-FTMW instrumentation have allowed the characterization of eleven and eight conformers for the neurotransmitters adrenaline and noradrenaline respectively. The observation of this rich conformational
behavior is in accordance with the recent observation of seven conformers for dopaminea and in sharp contrast with the
conformational reduction proposed for catecholamines.b
a C.
b H.
Cabezas, I. Peña, J. C. López, J. L. Alonso J. Phys. Chem. Lett. 2013, 4, 486.
Mitsuda, M. Miyazaki, I. B. Nielsen, P. ral,C. Dedonder, C. Jouvet, S. Ishiuchi, M. Fujii J. Phys. Chem. Lett. 2010, 1, 1130.
RK10
PROBING THE TAUTOMERISM OF HISTIDINE
10 min 3:57
C. BERMÚDEZ, C. CABEZAS, S. MATA, J. L. ALONSO, Grupo de Espectroscopía Molecular (GEM),
The rotational spectrum of histidine, showing a complex nuclear quadrupole interactions arising from three 14 N nuclei
in non-equivalent positions have been resolved and completely analyzed. Solid samples (m.p. 290 ◦ C) were vaporized
by laser ablation and probed by Fourier transform microwave spectroscopy in a supersonic expansion. The experimental
constants clearly lead to the unambiguous identification of the ε tautomer in the gas phase.
RK11
15 min 4:09
DEUTERIUM QUADRUPOLE COUPLING IN PROPIOLIC ACID AND FLUOROBENZENES MEASURED WITH
FTMW SPECTROMETER USING MULTIPLE FIDS a
MING SUN, BRYAN M. SARGUS, SPENCER J. CAREY and STEPHEN G. KUKOLICH, Department of
Chemistry and Biochemistry, The University of Arizona, Tucson, Arizona 85721..
Rotational spectra of deuterated propiolic acids (Pro-OD and Pro-CD), 1-fluorobezence (4-D), and 1,2-difluorobezence
(4-D) in their ground states have been measured using the newly constructed Fourier transform microwave (FTMW) spectrometer with 12" dia. mirrors and 5 kHz resolution. Multiple Free Induction Decays (FIDs) [up to 15] as well as background subtraction can be achieved with each beam pulse. For 1-fluorobezence (4-D), three hyperfine lines from the lowest
J=1-0 transition were measured to check the synthesis method. For 1,2-difluorobezence (4-D), we obtained 35 hyperfine
transitions from 3 to 12 GHz, including four different ∆J transitions. Deuterium quadrupole coupling along three the inertia axes was well resolved. For deuterated propiolic acids, 37 hyperfine lines of Pro-OD and 59 hyperfine lines of Pro-CD,
both including four different ∆J transitions, were obtained from 5 to 16 GHz. Deuterium quadrupole coupling along three
the inertia axes was well resolved for Pro-OD. For Pro-CD, only the eQqaa was determined due to the near-coincidence of
the CD bond and the a inertial axis.
a Supported
331
RK12
MICROWAVE SPECTRA OF FLUORINATED PROPIONIC ACIDS AND THEIR HYDRATES
15 min 4:26
DANIEL A. OBENCHAIN, G. S. GRUBBS II, STEWART E. NOVICK, Department of Chemistry, Wesleyan
University, Middletown, CT 06459; STEPHEN A. COOKE, School of Natural and Social Sciences, Purchase
College, SUNY, 735 Anderson Hill Road, Purchase, NY 10577; AGAPITO SERRATO III and WEI LIN, Department of Chemistry and Environmental Science, University of Texas at Brownsville, Brownsville, TX 78520.
The microwave spectra of three fluorinated propionic acids, namely pentafluoropropionic acid, 2,2,3,3-tetrafluoropropionic
acid, and 2,3,3,3-tetrafluoropropionic acid have been observed and assigned. The spectra of pentafluoropropionic acid and
its monohydrate were reported in this meeting last year. The conformational analysis of 2,2,3,3-tetrafluoropropionic acid
and 2,3,3,3-tetrafluoropropionic acid will be compared to that of pentafluoropropionic acid. The structures of the three
monohydrates will be discussed in terms of hydrogen bonding.
RK13
MW SPECTROSCOPY COUPLED WITH ULTRAFAST UV LASER VAPORIZATION:
SUCCINIC ACID IN THE GAS PHASE
10 min 4:43
ESTIBALIZ MENDEZ, PATRICIA ECIJA, EMILIO J. COCINERO, FERNANDO CASTANO, FRANCISCO J. BASTERRETXEA, Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Ap.644, E-48940, Bilbao, Spain; PETER D. GODFREY, DON MCNAUGHTON, School of Chemistry, Box 23 Victoria 3800 Monash University, Australia; MICHAELA K.
JAHN, K.P. RAJAPPAN NAIR, JENS-UWE GRABOW, Institut für Physikalische Chemie und Elektrochemie,
Gottfried-Wilhelm-Leibniz-Universität, 30167 Hannover, Germany.
Recent lab and field measurements have indicated critical roles of organic acids in enhancing new atmospheric aerosol
formation. In order to understand the nucleation process, here we report an experimental and theoretical investigation of
chemical structure of succinic acid. We have used the technique of Fourier Transform Microwave Spectroscopy (FTMW).
Succinic acid was vaporized by UV ultrafast laser ablation to suppress thermal decomposition processesa and seeded
into an expanding stream of Ne forming a supersonic jet. The rotational spectrum detected the presence of a single most
stable conformation in the cm- mm- wave regions for which accurate rotational and centrifugal distortion parameters
have been determined. The study was extended to all monosubstituted isotopic species (13 C, 18 O, D(O)), which were
positively identified, leading to an accurate determination of the effective and substitution structures of the molecule. The
experimental study was supplemented by ab initio (MP2) and DFT (M06-2X and B3LYP) calculations.
E. J. Cocinero, A. Lesarri, P. Écija, F. J. Basterretxea, J. U. Grabow, J. A. Fernández and F. Castaño, Angew. Chem. Int.
Ed., 51, 3119-3124, 2012.
a
RK14
15 min 4:55
CHIRPED-PULSE FOURIER TRANSFORM MICROWAVE SPECTROSCOPY OF 3-VINYLBENZALDEHYDE
MIRANDA SMITH and GORDON G. BROWN, Department of Science and Mathematics, Coker College,
300 E College Ave., Hartsville, SC 29550..
The pure rotational spectrum of 3-vinylbenzaldehyde (3VBA) has been measured and assigned. Coker College’s chirpedpulse Fourier transform microwave (CP-FTMW) spectrometer was used to measure the rotational spectrum of 3VBA in
the 7.5 - 18.5 GHz region of the microwave spectrum. The results have been analyzed to discover the rotational constants
and centrifugal distortion constants of four distinct conformations of 3VBA: cis,cis-, cis,trans-, trans,cis-, and trans,trans3VBA. The experimental rotational constants have been compared to the results of ab initio calculations. The performance
of Coker’s CP-FTMW spectrometer will also be discussed.
332
RK15
CHIRPED-PULSE
FOURIER
CHLOROBENZALDEHYDE
TRANSFORM
MICROWAVE
SPECTROSCOPY
10 min 5:12
OF
M ET A-
SEAN T. ARNOLD, JESSICA A. GARRETT, and GORDON G. BROWN, Department of Science and Mathematics, Coker College, 300 E College Ave., Hartsville, SC 29550..
The pure rotational spectrum of meta-chlorobenzaldehyde (m-ClBA) has been measured from 8 - 18.5 GHz by chirpedpulse Fourier transform microwave (CP-FTMW) spectroscopy. The spectrum has been analyzed to discover the presence
of two conformations of m-ClBA in the free jet expansion. For each conformation the rotational constants, the centrifugal
distortion constants, and the nuclear quadrupole coupling constants have been found for both the 35 Cl and the 37 Cl isotopologue. The rotational constants and the nuclear quadrupole coupling constants have been compared to ab initio calculations
performed using the Gaussian 03W software package.
RK16
15 min 5:24
ROTATIONAL SPECTRUM OF HEXAFLUOROISOPROPANOL AND COMAPRISION TO HEXAFLUOROISOBUTENE
ABHISHEK SHAHI, and E. ARUNAN, Department of Inorganic and Physical Chemistry, Indian Institute of
Science, Bangalore, India-560012.
Last yeara , the rotational spectra of hexafluoroisopropanol(HFIP) and its OD species was presented. Microwave spectra
of three more isotopologues of HFIP (two 13 C and one CD-OD) have now been recorded and fitted within experimental
uncertainty.Many new lines for the parent species have also been observed (making it to total 111 transitions for the
parent species). Previous IR studiesb show that the molecule exists in two conformers: antiperiplanar (AP) and synclinical
(SC). Ab initio calculations show that the AP conformer is more stable than the SC conformer. Moreover, AP conformer
has bc-plane of symmetry and thus has no a-dipole moment. The fitted rotational constants and absence of any a-type
transition confirm that the observed spectra correspond to the AP-conformer. Kraitchman’s analysis further support this
observation. There was no signature for the SC conformer however, nearly 35 lines still remain unassigned. Unlike the
similar molecule hexafluoroisobutenec, HFIP does not show any doubling in transitions though both the molecules have
very similar frequency for the puckering mode. Moreover, HFIP offers different posibilities for H-bonding and search for
its water complex is in progress. Details will be presented in the talk.
a A. Shahi, D. Mani and E. Arunan, Talk RH08, 67th International Symposium on Molecular Spectroscopy, The Ohio State University, Columbus, OH
(2012).
b H. Schaal, T. Häber, M. A. Suhm, J. Phys. Chem. A 104, 265 (2000).
c G. S. Grubbs, S. E. Novick, W. C. Pringle, E. J. Ocola and S. A. Cooke, J. Phys. Chem. A 116, 8169 (2012).
333
FA. ASTRONOMICAL SPECIES AND PROCESSES
FRIDAY, JUNE 21, 2013 – 8:30 AM
Chair: KYLE CRABTREE, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA
FA01
15 min 8:30
THE PUBLICLY AVAILABLE PREBIOTIC INTERSTELLAR MOLECULAR SURVEY (PRIMOS):
EXPANDING SPECTROSCOPIC CHARACTERIZATIONS, EXTENDING TO NEW SOURCES, AND ADDING TO
THE KNOWN MOLECULAR INVENTORY
BRETT A. McGUIRE, P. BRANDON CARROLL, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125; JOANNA F. CORBY, Department of Astronomy, University
of Virginia, Charlottesville, VA 22904; RYAN A. LOOMIS, Department of Chemistry, University of Virginia,
Charlottesville, VA 22904; GEOFFREY A. BLAKE, Division of Chemistry and Chemical Engineering and Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125; JAN M.
HOLLIS, NASA Goddard Space Flight Center, Greenbelt, MD 20771; FRANK J. LOVAS, National Institute
of Standards and Technology, Gaithersburg, MD 20899; PHILIP R. JEWELL, and ANTHONY J. REMIJAN,
National Radio Astronomy Observatory, Charlottesville, VA 22903.
The publicly available Green Bank Telescope PRebiotic Interstellar MOlecular Survey (PRIMOS) conducted towards Sgr
B2(N) provides high resolution, high-sensitivity observations with near-continuous frequency coverage from ∼300 MHz 50 GHz. Of the eleven new molecular detections in the last year, five (45%) are a direct result of the PRIMOS observations.
Further, these observations have recently been used to detect the predicted, but previously unobserved, J = 1 − 0 and
J = 2 − 1 transitions of the newly detected l-C3 H+ ion. Here, we discuss the analysis of these transitions, as well as recent
work to extend the PRIMOS observations to three new regions of interest: VY Canis Majoris, IRC+10216, and NGC 2023.
Finally, we highlight the utility of cm-wave surveys in new molecular detections, as well as the value of publicly-available
surveys in the approaching era of data-enabled, analysis-limited astrochemistry.
FA02
THE IONIZATION TOWARD THE HIGH-MASS STAR-FORMING REGION NGC 6334 I
15 min 8:47
J. MORALES, University of Puerto Rico, Rio Piedras Campus, Physics Department, San Juan, Puerto Rico
00931; C. CECCARELI, Institut de Planétologie et d’Astrophysique de Grenoble (IPAG) UMR 5274, Grenoble, F-38041, France; L. OLMI, Osservatorio Astrofisico di Arcetri - INAF, Largo E. Fermi 5, I-50125, Firenze,
Italy; D. LIS, California Institute of Technology, Pasadena, CA 91125, USA; R. PLUME, Department of
Physics and Astronomy, University of Calgary, Calgary, AB T2N 1N4, Canada; P. SCHILKE, I. Physikalisches Institut der Universität zu Köln, Zülpicher Str. 77, 50937 Köln, Germany.
In this work we present high-resolution spectral line observations carried out with the HIFI (Heterodyne Instrument for
the Far Infrared) instrument on board the Herschel Space Observatory (HSO) toward the so-called hot core NGC 6334 I,
a region of high-mass star formation. From the Herschel/HIFI observations of the molecular tracers C18 O, C17 O, HCO+ ,
H13 CO+ , and N2 H+ , we determined the line parameters of each of the rotational transitions, with Jup ≥ 5. With these
results, and using a non-Local Thermodynamic Equilibrium (LTE) Large Velocity Gradient (LVG) radiative transfer code,
we modeled the spectral line emission of the molecular transitions in order to estimate the temperature, H2 density, source
size, and CO, HCO+ and N2 H+ column density toward NGC 6334 I. We also derived the H2 column density as well
as the relative abundances between the various molecular species by using the results from the LVG analysis. Finally, by
modeling the chemical evolution of the source with a gas-phase reaction network, we obtained an estimate of the cosmic ray
ionization rate toward the region. Based on our results, we conclude that there is an expansion of the envelope surrounding
the hot core of NGC 6334 I, and the physical and kinematical properties of this expanding envelope are described in our
analysis.
334
FA03
15 min 9:04
ROTATIONAL SPECTRA OF ISOTOPIC CH3 CN IN THEIR v8 = 1 EXCITED VIBRATIONAL STATES
HOLGER S. P. MÜLLER, I. Physikalisches Institut, Universität zu Köln, 50937 Köln, Germany;
B. J. DROUIN, J. C. PEARSON, Jet Propulsion Laboratory, California Institute of Technology, Pasadena,
CA 91109, USA; A. BELLOCHE, K. M. MENTEN, Max-Planck Institut für Radioastronomie, 53121 Bonn,
Germany.
Methyl cyanide, CH3 CN, is an important interstellar molecule, in particular in hot and dense molecular cores, and it may
play a role in the atmospheres of planets or of Titan. Therefore, we have recorded extensive rotational spectra up to
∼ 1.6 THz. Ground state rotational transitions of a number of minor isotopologs could be identified up to 1.2 THz in
a
natural isotopic composition, including CH2 DCN and 13 CH13
3 CN.
13
15
Recently, we have analyzed the rotational spectra of CH3 CN, CH13
3 CN, and CH3 C N in their v8 = 1 excited vibrational states from spectra covering most of the frequencies between 0.44 THz and 1.20 THz. The analyses of the 15 N
and 13 C species were facilitated by previous data up to 144 GHz and 56 GHz, respectively. Spectroscopic parameters
determined in the fits will be compared with those of the main isotopolog.b The importance of these results, in particular
for radio-astronomical observations with the Atacama Large Millimeter Array (ALMA), will be stressed by the detection
of transitions pertaining to the 13 C species in Sagittarius B2(N).
a H.
b H.
S. P. Müller, B. J. Drouin, and J. C. Pearson, Astron. Astrophys. 506 (2009) 1187.
S. P. Müller et al., manuscript in preparation.
FA04
15 min 9:21
THE FIRST EXTENSIVE MOLECULAR STUDY OF AN OXYGEN-RICH PLANETARY NEBULA: OBSERVATIONS
OF SiO, SO2 , AND SO
A majority of stars will go through the Planetary Nebula (PN) phase during their stellar lifetimes, becoming significant
contributors to the chemical enrichment of the interstellar medium. Planetary Nebulae (PNe) in general are poorly understood, both physically and chemically. The PN M2-48 is an interesting candidate for study because not only is it clearly
oxygen-rich, but also because it has an age of ∼5,000 years; i.e. is about mid-way through the PN stage. Previous studies
of PNe have been in either very young (∼700-1,500 years) or very old (∼12,000 years) objects. Observations of M2-48
have been carried out with the Sub-Millimeter Telescope and the 12-meter Antenna of the Arizona Radio Observatory.
CO, CN, HCN, HNC, HCO+ , CS, SO, SO2 , and SiO have been detected. CS and SO were recently detected in the barely
oxygen-rich NGC 6537, but this is the first detection of SO2 and SiO in a PN. Indeed, age does not appear to dictate
PN chemistry, but rather the chemical makeup of the progenitor AGB star. Analysis is currently under way to model the
molecular abundances in this object. Most current results will be presented.
FA05
15 min 9:38
MAPPING THE MOLECULAR OUTFLOWS OF THE HIGH EXCITATION RED SPIDER NEBULA (NGC 6537)
The Red Spider nebula is a relatively young (∼1,600 years), very high excitation Planetary Nebula (PN). It is one of the
few PN that has been well classified in terms of its molecular content. A number of atomic emission lines, including
high energy ions like [Si IV] and [Ne V], as well as H2 and CO have been observed in this object. Remarkably, this very
hot nebula is chemically-rich, as indicated by our recent molecular detections of CN, HCN, HNC, CCH, CS, SO, H2 CO,
HCO+ and N2 H+ . Fractional abundances with respect to H2 range from f(X) ∼ 8 x 10−9 - 2 x 10−7 . In order to further
evaluate the extent of its chemical content and excitation conditions, a number of maps in multiple transitions of CO are
being made using the Sub-Millimeter Telescope of the Arizona Radio Observatory. A map of the J = 3 → 2 transition at
345 GHz (22 arcsecond resolution) is partially completed. A map of the J = 4 → 3 line at 461 GHz is also in progress
as well as measurements of the J = 6 → 5 transition near 691 GHz. These data will be analyzed to determine densities
and temperatures in this nebula. Preliminary findings suggest that CO emission is coincident with the optical image of the
“Red Spider”.
335
FA06
15 min 9:55
STRUCTURE OF THE DENSE MOLECULAR GAS IN THE HELIX NEBULA: LARGE SCALE MAPPING OF HCO+
N. R. ZEIGLER, L. M. ZIURYS, Department of Chemistry, University of Arizona, PO Box 210041, 1306
East University Blvd, Tucson, AZ, 85721, USA; L. N. ZACK, Department of Chemistry, University of Basel,
Klingelbergstrasse 80, CH-4056 Basel, Switzerland.
The Helix Nebula, NGC 7293, has been mapped in HCO+ J = 1 → 0 emission with a 70′′ spatial resolution (1.68 km
s−1 velocity resolution) using the Arizona Radio Observatory (ARO) 12 m telescope on Kitt Peak. Over 200 individual
positions covering an area of roughly 1000 × 800 ′′ were observed down to a 3σ noise level of ~20 mK. HCO+ was detected
at over three-quarters of the positions, with the majority of spectra showing multiple velocity components indicative of a
complex kinematic structure. The column density of HCO+ across the Helix ranges from Ntot Λ1.4 × 1011 toΛ2.4 ×
1012 cm−2 , with an average NtotΛ4 × 1011 cm−2 . The HCO+ distribution, which traces gas with densities ~105 cm−3 ,
is similar to that of CO and H2 , with certain point symmetries and red– and blue–shifted regions common in all three
molecules; these data are also consistent with observations of atomic lines. The HCO+ emission appears to trace two
ring-like structures emanating from the central star: one is blue-shifted and the other red-shifted with respect to the star,
and possibly trace the edges of a bipolar outflow.
Intermission
FA07
15 min 10:30
THE CM-, MM- AND SUBMM-WAVE SPECTRUM OF ALLYL ISOCYANIDE AND RADIOASTRONOMICAL OBSERVATIONS IN ORION KL AND THE PRIMOS LINE SURVEY
I. HAYKAL, R. A. MOTIYENKO, L. MARGULÈS, and T. R. HUET, Laboratoire PhLAM, UMR8523 CNRSUniversité Lille 1, F-59655 Villeneuve d’Ascq Cedex, France; P. ECIJA, E J. COCINERO, F BASTERRETXEA, J. A. FERNÁNDEZ, F. CASTANO, Departamento de Química Física, Facultad de Ciencia y
Tenología, Universidad del País Vasco, Barrio Sarriena s/n, 48940 Leioa (Spain); B. TERCERO, J. CERNICHARO, Centro de Astrobiología (CSIC-INTA). Ctra de Ajalvir, Km 4, 28850 Torrejón de Ardoz, Madrid,
Spain; A. LESARRI, Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47011 Valladolid (Spain); J. C. GUILLEMIN, Sciences Chimiques de Rennes -Ecole
Nationale Supérieure de Chimie de Rennes -CNRS -35700 Rennes, France.
Last year we presented the first rotational analysis of the ground state of the two conformers of allyl isocyanide from 4
GHz to 905 GHz. The analysis of the rotational spectrum of the cis conformer of allyl isocyanide was extended. We
resolved Coriolis interactions of a and b types between the excited vibrational states ν1 = 1 and ν2 = 1, calculated to be
′
′′
at 156 cm−1 (A ) and 167 cm−1 (A ) respectively (MP2/aug-cc-pvtz), from 150 GHz to 600 GHza . Strong perturbations
were observed in the 150-310 GHz range for low values of the quantum number Ka starting from Ka = 0, 1. The
anharmonicities appeared as well at higher frequencies for larger quantum numbers. The two modes were fitted together
with the SPFIT/SPCATb suite of programs and a set of Coriolis parameters was accurately determined. The fit contains
more than 3000 lines up to J = 99 and Ka = 12 for both modes. We did not detect these species neither in the IRAM
30-m line survey of Orion KL nor in the PRIMOS survey towards SgrB2. Nevertheless, we provided upper limits to their
column density in Orion KL. This work was supported by the CNES and the Action sur Projets de l’INSU, PCMI.
a I.
Haykal et al. manuscript in preparation
Pickett J. Mol. Spec.148, 371-377, 1991.
b H.
336
FA08
MILLIMETER-WAVE SPECTROSCOPY OF AMINOMALONONITRILE
15 min
10:47
ROMAN A. MOTIYENKO, LAURENT MARGULÈS, Laboratoire PhLAM, UMR 8523 CNRS - Université
Lille 1, 59655 Villeneuve d’Ascq Cedex, France; JEAN-CLAUDE GUILLEMIN, Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS - ENSCR, 35708 Rennes Cedex 7, France.
In low-temperature conditions of the interstellar medium pure HCN and mixtures of HCN with H2 O and NH3 subjected to
high-energy sources can be converted into different HCN polymersa. In this context the HCN trimer – aminomalononitrile
(AMN, H2 NCH(CN)2 ) is an interesting candidate for astrophysical detection.
We measured the rotational spectrum of AMN using the Lille BWO-based fast scan spectrometer (120 – 180 GHz) and the
spectrometer based on solid state sources (225 – 250 GHz). The spectroscopic work was supported by high level ab initio
calculations. The spectra observed were assigned only to the asymmetric conformer. The first analysis revealed the regular
doublet splittings of rotational lines indicating the possibility of large-amplitude motion (LAM) of amino group. Further
examination of the spectra revealed the existence of additional splittings most probably due to the second LAM of amino
group. Since the equilibrium structure of AMN has no symmetry, in the group theoretical formalism these two LAMs
can be described using G4 permutation-inversion group. Despite the complexity of the LAMs all the assigned rotational
transitions were fitted within experimental accuracy using Pickett’s SPFIT program. As a result, a reliable dataset for
astrophysical observations was provided.
This work is supported by the french program "Physique et Chimie du Milieu Interstellaire (PCMI, INSU-CNRS)" and the
Centre National d’Etudes Spatiales (CNES).
a Gerakines,
P.A., Moore, M.H, Hudson, R.L., Icarus, 2004, 170, 203
FA09
15 min 11:04
TORSION-ROTATION-VIBRATION EFFECTS IN THE ν20 , 2ν21 , 2ν13 AND ν21 + ν13 STATES OF CH3 CH2 CN
ADAM M. DALY, JOHN C. PEARSON, SHANSHAN YU, BRIAN J. DROUIN, Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Dr., Pasadena, CA 91109; C. BERMÚDEZ, J. L.
ALONSO, Grupo de Espectroscopia Molecular (GEM), Edificio Quifima, Laboratorios de Espectroscopia y
Bioespectroscopia, Parque Cientfíco, Universidad de Valladolid, 47011 Valladolid, Spain.
Ethyl cyanide, CH3 CH2 CN, is a highly abundant molecule in hot cores associated with massive star formation where
temperatures often approach 200K. Astrophysicists would like to use the many thousands of observed lines to evaluate
thermal equilibrium, temperature distributions, heating sources, and radiative pumping effects. In spite of a recent partial
success in characterizing the ν20 and ν12 vibrational statesa , many aspects of the spectroscopy of the ν20 state are not
adequately characterized. Torsional splittings in the b-type spectrum of ν20 are typically a few MHz and many a-type
transitions also show resolved torsional splittings, both are incompatible with the expected 1200 cm−1 barrier to internal
rotation in a vt = 0 state. Additionally all K values above 2 show some obvious perturbations. The three states that lie just
above ν20 are 2ν21 , 2ν13 and ν21 + ν13 . It has been determined that ν20 interacts weakly with both 2ν21 and 2ν13 and that
2ν21 interacts weakly with 2ν13 , in spite of their common symmetry and very close proximity. However, all the interactions
of ν21 +ν13 appear to be very strong, making assignments of the combination band particularly problematic. The numerous
interactions result in wide spread anomalous torsional splittings. These splittings provide valuable insight into the nature of
the interactions, however without a reasonable model, assignment of A or E to a torsional component is far from obvious.
There remains no reasonable quantum mechanical description of how to proceed with a torsion-rotation-vibration analysis
involving large and small amplitude motions. Regardless, everything that can be assigned in the laboratory spectrum can
be securely identified in the astronomical spectrum of several sources, suggesting that a solution to this problem is needed.
We present what is known and unknown in this quartet of CH3 CH2 CN states.
a Daly,
Bermúdez, Lopez, Tercero, Pearson, Marcelino, Alonso, and Cernicharo, Astrophys. J. (2013) in press.
337
FA10
MILLIMETER- WAVE SPECTRUM OF CARBONYL DIAZIDE IN PURSUIT OF DIAZIRINONE
15 min
11:21
BRENT K. AMBERGER, BRIAN J. ESSELMAN, R. CLAUDE WOODS and ROBERT J. McMAHON, The
University of Wisconsin - Madison Department of Chemistry, 1101 University Avenue, Madison, WI 53705.
Pyrolysis of carbonyl diazide (CO(N3 )2 ) has been shown to give diazirinone (CON2 ).a While diazirione decomposes
over the course of a few hours under terrestrial conditions, there is the possibility for it to exist in space. In the pursuit of
obtaining a rotational spectrum for diazirinone, we have started with the rotational spectroscopy of its immediate precursor,
carbonyl diazide. Carbonyl diazide is highly explosive, and requires careful synthesis.b Spectra in the range of 260-360
GHz were collected at room temperature and at −60◦C. Ab initio calculations at the CCSD/cc-pVDZ level predict that the
conformation where both azide groups are syn to the carbonyl is preferred. A second conformation, where one azide is syn
and one is anti, is calculated to lie about 2 kcal/ mol higher in energy. Pure rotational transitions for the ground state and
multiple low-lying excited vibrational states of the syn- syn conformation are readily observed and assigned.
a X.
Zeng, H. Beckers, H. Willner and J. F. Stanton, Angew. Chem. Int. Ed. 50 (2011), 1720-1723
M. Nolan, B. K. Amberger, B. J. Esselman, V. S. Thimmakondu, J. F. Stanton, R. C. Woods, and R. J. McMahon, Inorg. Chem. 51 (2012),
9846-9851
b A.
FA11
MILLIMETER- WAVE SPECTRUM OF PYRIDAZINE
15 min
11:38
BRENT K. AMBERGER, BRIAN J. ESSELMAN, JOSH D. SHUTTER, R. CLAUDE WOODS and
ROBERT J. McMAHON, The University of Wisconsin - Madison Department of Chemistry, 1101 University Avenue, Madison, WI 53705.
Pyridazine, the ortho dinitrogen substituted analogue of benzene, was chosen as an inaugural project for our newly modernized millimeter-wave absorption spectrometer. Pyridazine has a substantial dipole of 4.22 debye, and is thus a candidate
for astronomical detection. If detected, it would be among the first 6π electron aromatic systems to be observed in space.
Spectra in the range of 260-360 GHz were collected at room temperature. Pure rotational spectra for 10 vibrational states
and 4 naturally occurring isotopomers are assigned and reported. Among the vibrationally excited states, both Coriolis and
Fermi coupling is observed. Anharmonic vibration-rotation calculations using the CFOUR package are used to find and
assign transitions for the vibrationally excited states. These calculations at the CCSD(T)/cc-pVTZ level provide excellent
predictions for the rotational constants of these excited states.
FA12
15 min
A LABORATORY SEARCH FOR THE CARRIER OF U-LINES ATTRIBUTED TO l-C3 H
NEBULA PDR
+
11:55
IN THE HORSEHEAD
MICHAEL C. McCARTHY, KYLE N. CRABTREE, and OSCAR MARTINEZ, JR., Harvard-Smithsonian
Center for Astrophysics, Cambridge, MA 02138.
Recent radio observations of the Horsehead nebula PDR in the millimeter-wave band by Pety et al.a detected a series
of unidentified lines which have been attributed to l-C3 H+ , a molecular cation for which no high-resolution laboratory
data presently exist. We have detected a pair of rotational lines in the centimeter-wave band at frequencies predicted from
their derived spectroscopic constants using Fourier transform microwave and microwave-microwave double resonance
spectroscopies. Experimental evidence strongly suggests that the laboratory and astronomical lines arise from a common
carrier, and that the carrier is a closed-shell, reactive hydrocarbon containing a linear or nearly-linear three carbon atom
backbone.
a Pety
et al. Astron. & Astrophys. 548, A68 (2012).
338
FB. MINI-SYMPOSIUM: THEORY AND SPECTROSCOPY
FRIDAY, JUNE 21, 2013 – 8:30 AM
Chair: STEPHEN COY, Massachusetts Institute of Technology, Cambridge, MA
FB01
INVITED TALK
ROTATIONAL SPECTROSCOPY MEETS THEORY
30 min 8:30
CRISTINA PUZZARINI, Dipartimento di Chimica "G. Ciamician", Università di Bologna, I-40126 Bologna,
Italy.
Rotational spectroscopy is known to be a technique widely used to infer information on molecular structure and dynamics.
In the last decades, its role in the field of atmospheric and astrophysical investigations has rapidly grown up. However,
several are the challenging aspects in rotational spectroscopy, since the detection and analysis of spectra as well as interpretation of obtained results are not at all straightforward. Quantum chemistry has reached such an accuracy that can be used
to disentangle these challenging situations by guiding the experimental investigation, assisting in the determination of the
spectroscopic parameters, and extracting information of chemical interest. This presentation provides an overview of the
theoretical background and computational requirements needed for the accurate evaluation of the spectroscopic parameters
of relevance to rotational spectroscopy. The role of theory in guiding and supporting experiment is detailed through a few
examples and the interplay of experiment and theory is discussed in terms of the information of physical and chemical
interest that can be derived.
FB02
15 min 9:05
ANALYSIS OF THE MICROWAVE SPECTRUM OF THE THREE-TOP MOLECULE TRIMETHOXYLMETHANE
Créteil, France; G. FENG, AND W. CAMINATI, Dipartimento di Chimica “G. Ciamician," Università di
Bologna, Via F. Selmi, 40126 Bologna, Italy.
Although many investigations about the spectrum of molecules displaying internal rotation of one or two methyl tops have
been reported, there are much fewer results about the spectrum of molecules with three methyl tops.
In this paper, we will deal with the microwave spectrum of trimethoxylmethane, HC(OCH3 )3 , a molecule displaying three
conformers of quite different symmetry which all exhibit internal rotation of their three methyl tops. In a first step, a
theoretical approach dedicated to the calculation of the rotation-torsion energy levels of a molecule with three inequivalent
tops was developed. The model is based on a DVR approach;a it accounts accurately for the rotation-torsion Coriolis
couplings due to the torsion of each methyl top and leads to matrices which are smaller than those arising with the usual
free internal rotation functions. The theoretical approach shows that internal rotation of the three tops leads to 27 tunneling
sublevels, including 13 doubly degenerate ones. The statistical weights of the sublevels are 24 , 25 , and 26 .
The microwave spectrum of trimethoxylmethane has been recorded from to 10 to 19 GHz with the molecular beam Fourier
transform spectrometer of the University of Bologna. The spectra of the TMM1, TMM2, and TMM3 conformers with C1 ,
C3 , and Cs symmetry, respectively, have been observed. The theoretical model has been applied to the lowest lying TMM1
conformer since it is the only one with three inequivalent methyl tops. The parameters describing the rotational energy and
the rotation-torsion Coriolis couplings were obtained from the geometry of the conformer and those corresponding to height
of the barriers hindering the internal rotations were retrieved through ab initio calculations. Calculated tunneling patterns
were compared to experimental ones. As far as the number of tunneling components is concerned, there is a qualitative
agreement between experiment and theory. However, the present calculation seems to underestimate the various tunneling
splittings and this probably due to the fact that the barrier heights obtained through ab initio calculations are too high.
a Light
and Bačić, J. Chem. Phys. 87 (1987) 4008.
339
FB03
15 min 9:22
EXTENSION OF THE MEASUREMENT, ASSIGNMENT, AND FIT IN THE GROUND STATE OF THE TWO-TOP
MOLECULE METHYL ACETATE
H. V. L. NGUYEN, I. KLEINER, Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), UMR
7583 (CNRS/Univ. Paris Est et Paris Diderot), Université de Paris Est, 61 avenue du Général de Gaulle,
F-94010 Créteil cedex, France; S. SHIPMAN, Division of Natural Sciences, New College of Florida, 5800
Bay Shore Road, Sarasota, FL 34243-2109, USA; and K. KOBAYASHI, Department of Physics, Faculty of
Science, Toyama University, 3190 Gofuku Toyama, Toyama, 930-8555, Japan.
New spectroscopic data were recorded for the two-top molecule methyl acetate with a chirped-pulse Fourier transform
microwave spectrometer at room temperature and a jet cooled sub-millimeterwave spectrometer. More than 650 new lines
with J up to 35 and K up to 15 were assigned. In total, approximately 1500 lines were fitted with 34 parameters using
the program BELGI-Cs -2tops to a standard deviation close to the measurement error. More precise determinations of the
top-top interaction and the J, K dependent parameters as well as the influence of the total rotation on the top-top interaction
were carried out. The extension of the ground state spectrum of methyl acetate is a necessary step before searching for the
first torsional excited transition in both torsional modes in the room temperature spectrum.
FB04
15 min 9:39
A FITTING PROGRAM FOR MOLECULES WITH TWO EQUIVALENT TOPS AND C2V POINT-GROUP SYMMETRY AT EQUILIBRIUM: APPLICATION TO EXISTING MICROWAVE, MILLIMETER, AND SUB-MILLIMETER
WAVE MEASUREMENTS OF ACETONE
VADIM V. ILYUSHIN, Institute of Radio Astronomy of NASU, Chervonoproporna 4, 61002 Kharkov,
Ukraine. NIST Guest Worker June - August 2009.; JON T. HOUGEN, Sensor Science Division, National
Institute of Standards and Technology, Gaithersburg, MD 20899-8441, USA.
We will present a new theoretical tool, a program called PAM-C2v-2tops, for analysis of the high-resolution torsion-rotation
spectra of molecules with two equivalent methyl rotors and C2V symmetry at equilibrium. The new tool belongs to the
broad class of effective Hamiltonians, is based on Longuet-Higgins’ group theoretical ideas and uses G36 permutationinversion group-theoretical considerations, the principal axis method and a two-step diagonalization procedure. The program was used to carry out a weighted least-squares fit of 1720 microwave, millimeter-wave, and sub-millimeter-wave line
frequencies of acetone [(CH3 )2 CO] that are available in the literature. The weighted root-mean-square deviation of 0.93
obtained for a joint fit of the microwave lines belonging to the ground, the lower torsional fundamental, and the higher torsional fundamental states of acetone represents significant progress in comparison with previous fitting attempts, especially
for the excited torsional states.
FB05
15 min 9:56
GAS PHASE ROVIBRATIONAL SPECTROSCOPY OF DMSO, PART.I: WHEN A SYNCHROTRON SOURCE REVEALS AN UNUSUAL ROTATIONAL BEHAVIOUR
ARNAUD CUISSET, DMITRII A. SADOVSKII , Laboratoire de Physico-Chimie de l’Atmosphère, 189A
Ave. Maurice Schumann, 59140 Dunkerque, France; OLIVIER PIRALI, Ligne AILES, synchrotron SOLEIL,
L’Orme des Merisiers, Saint Aubin, BP 48, 91192 Gif-sur-Yvette, France..
Many of us have enjoyed the spectacle of a spinning top influenced by friction: rotating rapidly about a stable stationary
axis, the top loses slowly its angular momentum j (and energy), slows down gradually, and then, suddenly, its axis becomes
unstable, the top wobbles, and an abrupt change of the top’s position follows. In other words, the system undergoes a
bifurcation. In the case of the tippe top, rotation about its lower point is stable at low values of angular momentum J and
becomes unstable at large J. Something quite similar occurs in a freely rotating dimethylsulfoxyde (DMSO, (CH3 )2 SO)
molecule. For the first time in such large polyatomic molecule a quantum bifurcation induced by a gyroscopic destabilization was observed. a This unusual phenomenon in rotational dynamics was discovered in the rovibrational states of the
bending fundamental ν23 band of DMSO whose high-resolution gas phase absorption spectrum was observed along with
that of ν11 by Cuisset et al. b using the exceptional properties of the AILES beamline in the Far-Infrared domain. c
a A.
Cuisset, O. Pirali, D. Sadovskii,Phys. Rev. Lett., 109,(094101), 2012.
Cuisset, L. Nanobashvili, I. Smirnova, R. Bocquet, F. Hindle, G. Mouret, O. Pirali, P. Roy, D. Sadovskii,Chem. Phys. Lett., 492,(30),2010
c J. B. Brubach et al., AIP Conf. Proc., 1214, (81), 2010.
b A.
340
FB06
15 min 10:13
GAS PHASE ROVIBRATIONAL SPECTROSCOPY OF DMSO, PART II: TOWARDS THE TERAHERTZ OBSERVATION OF 4-FOLD CLUSTERS
ARNAUD CUISSET, MARIE-ALINE MARTIN-DRUMEL, FRANCIS HINDLE, GAEL MOURET,
DMITRII A. SADOVSKII , Laboratoire de Physico-Chimie de l’Atmosphère, 189A Ave. Maurice Schumann,
59140 Dunkerque, France.
Benefiting of the exceptional properties of the AILES synchrotron beamlinea, the gas phase Far-IR spectrum of DMSO has
been recorded and resolved b . The rovibrational analysis allowed to discover a new rotational behaviour for a polyatomic
molecule: the gyroscopic destabilization. c In order to explain this phenomenon, we looked for four-fold energy clusters
in the high resolution ground state THz spectrum of DMSO recorded with a sub-THz spectrometer based on a frequency
multiplication chain d . Pure rotational lines in the 5 lowest vibrationnally excited levels have been recorded below 700 GHz.
With near 1000 rotational transitions assigned, high quantum numbers have been reached allowing to discover sequence
of four-fold clusters in the out of plane bending mode of DMSO and to study the vibrational dependence of an unusual
rotational dynamics.
a J.
B. Brubach et al., AIP Conf. Proc., 1214, (81), 2010.
Cuisset, L. Nanobashvili, I. Smirnova, R. Bocquet, F. Hindle, G. Mouret, O. Pirali, P. Roy, D. Sadovskii,Chem. Phys. Lett., 492,(30),2010
c A. Cuisset, O. Pirali, D. Sadovskii,Phys. Rev. Lett., 109,(094101), 2012.
d G. Mouret, M. Guinet, A. Cuisset, L. Croizet, S. Eliet, R. Bocquet, F. Hindle, IEEE Sensors Journal, 13, 1, 2013.
b A.
Intermission
FB07
WHAT IS THE NATURE OF THE DOUBLETS IN THE E-METHANOL LAMB-DIP SPECTRA?
15 min
10:45
S. P. BELOV, A.V. BURENIN, G. Yu. GOLUBIATNIKOV and A.V. LAPINOV, Institute of Applied Physics
of RAS, 46 Ul’yanova str., GSP-120, Nizhny Novgorod 603950, Russia.
A large number of methanol lines have been measured with a Lamb-dip technique in the frequency range 75-510 GHz. A
few series of doublets for the transitions with selection rules ∆J = 0, ∆K = ± 1, ± 3, ± 5, E1 ↔ E2 and ∆J = ± 1,
∆K = ± 1 between the torsional-rotational levels of E-methanol in the νt = 0 state have been observed. These doublets
were not predicted and were not observed earlier. In a traditional approach to the methanol molecule (as a nearly prolate
asymmetric top with an internal rotation) these doublets may only originate from the magnetic hyperfine structure of the
E-methanol torsional-rotational levels. However, there are some signs in spectra indicating that the doublets are sensitive
to the parity selections rules. If so, the origin of the doublets is an inversion splitting of the E(+) and E(−) energy levels.
This exciting interpretation seems to be feasible. The results of the experimental measurements will be presented and the
possibility of a new type of the inversion motion in the CH3 OH molecule due to the proton tunneling in the H-O-C-H plane
will be discussed .
341
FB08
15 min 11:02
ROTATIONAL SPECTROSCOPY AND QUANTUM CHEMICAL CALCULATIONS OF A FRUIT ESTER: THE MICROWAVE SPECTRUM OF n-BUTYL ACETATE
T. ATTIG, L.W. SUTIKDJA, R. KANNENGIEßER, W. STAHL, Institute of Physical Chemistry, RWTH
Aachen University, Landoltweg 2, D-52074 Aachen, Germany; I. KLEINER, Laboratoire Interuniversitaire
des Systèmes Atmosphériques, CNRS et Universités Paris Diderot et Paris Est, 61 av. Général de Gaulle,
94010, Créteil, France.
In the course of our studies on a number of aliphatic ester molecules and natural substances, the rotational spectrum of
n-butyl acetate (CH3 -COO-C4 H9 ) has been recorded for the first time in the 10-13.5 GHz frequency range, using the
MB-FTMW spectrometer in Aachen, with an instrumental uncertainty of a few kHz for unblended lines.
Three conformers were observed. The main conformer with C1 symmetry has a strong spectrum. The other two conformers
have Cs and C1 symmetries. Their intensities are considerably weaker. The quantum chemical calculations of specific
conformers were carried out at the MP2/6-311++G(d,p) level, and for the main conformer different levels of theory were
calculated. To analyze the internal rotation of the acetyl methyl groups the codes XIAM (based on the Combined Axis
Method) and BELGI (based on the Rho-Axis-Method) were used to model the large amplitude motion. The molecular
structures of the three conformers were determined and the values of the experimental rotational constants were compared
with those obtained by ab initio methods. For all conformers torsional barriers of approximately 100 cm−1 were found.
This study is part of a larger project which aims at determining the lowest energy conformers and their structures of organic
esters and ketones which are of interest for flavour or perfume synthetic applicationsa.
a Project
partly supported by the PHC PROCOPE 25059YB
FB09
HIGH RESOLUTION THZ AND FIR SPECTROSCOPY OF SOCl2
15 min
11:19
M. A. MARTIN-DRUMEL, A. CUISSET, D. A. SADOVSKII, G. MOURET, F. HINDLE, Laboratoire de
Physico-Chimie de l’Atmosphère, EA 4493, Université du Littoral Côte d’Opale, 59140 Dunkerque, France;
O. PIRALI, Institut des Sciences Moléculaires d’Orsay, CNRS, UMR 8214, Université Paris XI, bât. 210,
91405 Orsay Cedex, France; SOLEIL Synchrotron, AILES beamline, L’orme des Merisiers, Saint-Aubin,
91192 Gif-Sur-Yvette, France.
Thionyl chloride (SOCl2 ) is an extremely powerful oxidant widely used in industrial processes and playing a role in the
chemistry of the atmospherea. In addition, it has a molecular configuration similar to that of phosgene (COCl2 ), and
is therefore of particular interest for security and defense applications. Low resolution vibrational spectra of gas phase
SOCl2 b as well as high resolution pure rotational transitions up to 25 GHzc have previously been investigated. To date no
high resolution data are reported at frequencies higher than 25 GHz.
We have investigated the THz absorption spectrum of SOCl2 in the spectral region 70–650 GHz using a frequency multiplier chain coupled to a 1 m long single path cell containing a pressure of about 15 µbar. At the time of the writing, about
8000 pure rotational transitions of SO35 Cl2 with highest J and Ka values of 110 and 50 respectively have been assigned
on the spectrum.
We have also recorded the high resolution FIR spectra of SOCl2 in the spectral range 50–700 cm−1 using synchrotron
radiation at the AILES beamline of SOLEIL facility. A White-type cell aligned with an absorption path length of 150 m
has been used to record, at a resolution of 0.001 cm−1 , two spectra at pressures of 5 and 56 µbar of SOCl2 . On these
spectra all FIR modes of SOCl2 are observed (ν2 to ν6 ) and present a resolved rotational structure. Their analysis is in
progress.
a T.
J. Johnson et al., J. Phys. Chem. A 107, 6183 (2003)
E. Martz and R. T. Lagemann, J. Chem. Phys. 22,1193 (1954)
c H. S. P. Müller and M. C. L. Gerry, J. Chem. Soc. Faraday Trans. 90, 3473 (1994)
b D.
342
FB10
STRUCTURE OF THE BENZENE DIMER—GOVERNED BY DYNAMICS
15 min
11:36
MELANIE SCHNELL, Center for Free-Electron Laser Science, 22761 Hamburg, Germany; Max-PlanckInstitut für Kernphysik, 69117 Heidelberg, Germany; UNDINE ERLEKAM, GERT VON HELDEN,
GERARD MEIJER, Fritz-Haber-Institut der Max-Planck-Gesellschaft, 14195 Berlin, Germany;
PHILIP R. BUNKER, National Research Council of Canada, Ottawa, Ontario K1A 0R6, Canada;
JENS-UWE GRABOW, Institut für Physikalische Chemie und Elektrochemie, Gottfried-Wilhelm-LeibnizUniverstät, 30167 Hannover, Germany; AD VAN DER AVOIRD, Institute for Molecules and Materials,
Radboud University, 6525 AJ Nijmegen, The Netherlands.
The benzene dimer is the prototype system for Van der Waals interactions between aromatic molecules. Here, we report a joint experimental and theoretical study a regarding normal (C6 H6 )2 and the partially deuterated (C6 D6 )(C6 H6 )
isotopologue. Interestingly, although its tilted T-shaped equilibrium structure corresponds to an asymmetric rotor, both
isotopologues exhibit the rotational

Abstract Book - International Symposium on Molecular Spectroscopy

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