docASPARAGINA EN FASE GAS POR ESPECTROSCOPÍA DE
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ASPARAGINA EN FASE GAS POR ESPECTROSCOPÍA DE
Rotational spectroscopy of metallic acetylides C. Cabezas, I. Peña , S. Mata, A. M. Daly, A. Martín, J. L. Alonso and J. Cernicharo* Grupo de Espectroscopia Molecular, Unidad Asociada CSIC Laboratorios de Espectroscopia y Bioespectroscopia Edificio Quifima. Parque Científico Universidad de Valladolid * Centro de Astrobiología CAB, CSIC–INTA II National Conference on Laboratory and Molecular Astrophysics INTEREST IN METALLIC ACETYLIDE SPECIES M-C≡C-H • Organic Synthesis (LiCCH, CuCCH, NaCCH) • Astrophysics as potential interstellar molecules Acetylenic species (CCH, C3H, C4H) abundant in space Found both in C-rich circumstellar shells and molecular clouds Metal-containing molecules have been found (AlCl, NaCl, AlF, KCl…) • Microwave spectroscopy perhaps best method of study Accurate structures for radio astronomy • Rotational studies of Metal Monoacetylides • Li, Na, K, Ca, Mg, Sr, Zn and Cu • Problems with generation, unstable species, explosive… • Characterization studies of AlCCH and AgCCH by FTMW spectroscopy II National Conference on Laboratory and Molecular Astrophysics EXPERIMENTAL REQUIREMENTS Generation Laser ablation-discharge source Precursors: *Solid rods of Aluminum and/or Silver *Mixture of 0.3% HCCH in Ne II National Conference on Laboratory and Molecular Astrophysics EXPERIMENTAL REQUIREMENTS Generation Characterization Laser ablation-discharge source 1 2 MB-FTMW spectroscopy1 and CP-FTMW spectroscopy2 C. Cabezas, S. Mata, A. M. Daly, A. Martín, J. L. Alonso and J. Cernicharo J. Mol. Spectr. 278 (2012) 31-34 S. Mata I. Peña, C. Cabezas, J. C. López and J. L. Alonso. J. Mol. Spectr. 280 (2012) 91–96 EXPERIMENT Gas pulse Laser pulse DC pulse Ne + 0.3% C2H2 Jet Metal sample Diffusion pump Rotary Nd:YAG laser Laser II National Conference on Laboratory and Molecular Astrophysics EXPERIMENT Gas pulse Laser pulse DC pulse FT-MW spectrometer Ne + 0.3% C2H2 Polarization Chirped MW pulse MW field Diffusion pump Rotary II National Conference on Laboratory and Molecular Astrophysics EXPERIMENT Gas pulse Laser pulse FT-MW spectrometer Ne + 0.3% C2H2 DC pulse Chirped MW pulse Molecular emission Detection Detection Diffusion pump Rotary FT Time-domain Frequency-domain AlCCH STUDY F=7/2-5/2 CP-FTMW spectrum F=3/2-5/2 F=5/2-5/2 J=1-0 40000 signal averages 9940 9200 9400 9600 9800 10000 10200 II National Conference on Laboratory and Molecular Astrophysics 10400 10600 9945 9950 9955 9960 9965 9970 J´ J´´ F´ F´´ ν obs. ν obs.-ν cal. 1 0 2.5 3.5 1.5 2.5 2.5 2.5 9945.3770 9954.2959 9958.0839 0.000 -0.001 0.002 2 1 3.5 1.5 4.5 3.5 0.5 2.5 3.5 1.5 3.5 2.5 1.5 2.5 19896.9981 19901.3596 19905.1961 19905.9194 19906.7960 19908.0242 0.000 0.002 -0.001 0.001 -0.004 0.002 AlCCH STUDY F=7/2-5/2 CP-FTMW spectrum F=3/2-5/2 F=5/2-5/2 J=1-0 40000 signal averages 9940 9945 9950 9955 Parameter 9200 9400 9600 9800 10000 10200 10400 10600 9965 Experimental B / MHz 4976.08620 (78) D / kHz 2.18 (10) eQq (Al) / MHz -42.3917 (65) CI / kHz 5.18 (30) rms / kHz 2.0 a II National Conference on Laboratory and Molecular Astrophysics 9960 B3LYP/aug-cc-pVTZ. 9970 Theor. 4911.89 a -46.64 a AgCCH STUDY MB-FTMW spectrum AgCCH AgCCH 107 J=1-0 107 109 AgCCH AgCCH J´ J´´ 1 2 3 0 1 2 ν obs. ν obs.-ν cal. ν obs. ν obs.-ν cal. 6394.5672 12789.1144 19183.6241 0.000 0.000 0.000 6373.9502 12747.8825 19121.7729 -0.001 0.001 0.000 107 Parameter 6372 6373 6374 6393 6394 6395 B / MHz D / kHz rms / kHz 6396 a Ag 109 AgCCH Experimental Theor. 3197.28504 (181) 3165.64 a 0.799 (120) 0.2 109 Experimental 3186.97714 (181) 0.832 (120) 0.6 B3PW91/genECP C From the isotopic rotational constants Ag-C bond distance can be estimated r (Ag-C) ≈ 2.02 Å II National Conference on Laboratory and Molecular Astrophysics AgCCH Theor. 3155.41a NaCl VIBRATIONAL STATES II National Conference on Laboratory and Molecular Astrophysics NaCl VIBRATIONAL STATES CP-FTMW with Laser Ablation-Discharge source 40000 signal averages 35 Na Cl J=1-0 5/2,3-3/2,2 5/2,4-3/2,3 5/2,2-3/2,2 37 1/2,2-3/2,1 1/2,2-3/2,3 3/2,1-3/2,0 3/2,1-3/2,2 1/2,1-3/2,2 1/2,1-3/2,0 3/2,3-3/2,3 3/2,2-3/2,1 3/2,2-3/2,3 5/2,1-3/2,1 3/2,0-3/2,1 13023.0 Na Cl 13024.5 13026.0 13027.5 13029.0 13020 13030 MB-FTMW spectrum 6000 8000 10000 II National Conference on Laboratory and Molecular Astrophysics 12000 14000 16000 18000 NaCl VIBRATIONAL STATES CP-FTMW with Laser Ablation-Discharge source 35 Na Cl 37 Na Cl 6000 12200 8000 12300 10000 12000 12400 12500 12600 II National Conference on Laboratory and Molecular Astrophysics 14000 16000 12700 12800 12900 18000 13000 NaCl VIBRATIONAL STATES CP-FTMW with Laser Ablation-Discharge source v=0 37 v=0 v=1 v=2 v=1 v=3 v=5 12200 12200 12300 37 37 v=4 35 v=4 v=5v=7 35 37 v=2 12300 12400 12500 II National Conference on Laboratory and Molecular Astrophysics 37 v=3 37 35 35 v=3 v=6 12400 12700 12600 37 37 v=2 35 35 35 v=5 35 12500 12900 12600 12800 13000 35 NaCl VIBRATIONAL STATES 5/2,3-3/2,2 5/2,4-3/2,3 5/2,2-3/2,2 3/2,1-3/2,0 3/2,1-3/2,2 MB-FTMW spectrum 1/2,2-3/2,1 1/2,2-3/2,3 3/2,3-3/2,3 3/2,2-3/2,1 3/2,2-3/2,3 1/2,1-3/2,2 1/2,1-3/2,0 v=2 37 3/2,0-3/2,1 12452.0 12453.5 12455.0 12456.5 v=3 12458.0 v=4 v=5 12200 37 12300 II National Conference on Laboratory and Molecular Astrophysics v=7 37 v=5 37 35 12400 v=6 35 35 12500 12600 ACKNOWLEDGEMENTS CSD 2009-00038 Molecular Astrophysics Grant CTQ 2010- 19008 Grant VA070A08 II National Conference on Laboratory and Molecular Astrophysics