69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 CH 4, C 2 H 4, SF 6 AND CF 4 CALCULATED SPECTROSCOPIC DATABASES FOR THE VIRTUAL ATOMIC AND MOLECULAR DATA CENTRE V. BOUDON, Ch. WENGER, R. SURLEAU, M. LOUVIOT, M. FAYE, Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS- Université de Bourgogne, 9. Av. A. Savary, BP 47870, F Dijon Cedex, France M. ROTGER, L. DAUMONT, D. A. BONHOMMEAU, Vl. G. TYUTEREV, Groupe de Spectrométrie Moléculaire et Atmosphérique (GSMA), CNRS UMR7 331, Université de Reims Champagne-Ardenne, Moulin de la Housse, B.P.1039, F Reims Cedex 2, France Y. A. BA, M.-L. DUBERNET, LERMA2, CNRS UMR8812, Observatoire de Paris, 5 Place Janssen, Meudon LERMA2

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 Contents I.Virtual Atomic and Molecular Data Centre II.Methane, CH 4 III.Ethylene, C 2 H 4 IV.Sulfur hexafluoride, SF 6 & Carbon tetrafluoride, CF 4 V.Conclusion and perspectives

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 I. Virtual Atomic and Molecular Data Centre

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 Dadabases Line list construction for HITRAN and GEISA (with Linda Brown, determination of semi-empirical upper states) Dijon spectroscopic analyses and databases Experimental data Global modelling SPVIEW interface FP7 – Research Infrastructures Global e-Infrastructure European project Global portal « Modern » database Data traceability In Dijon : Server with calculated CH 4 lines Fits and calculations XTDS interface Line lists Positions, intensities, collisional parameters, accuracy Since 2012 : OSU « THETA » Terre-Homme-Environnement-Temps- Astronomie

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 Virtual Atomic and Molecular Data Centre The Dijon group hosts 3 databases on a dedicated server: MeCaSDa (CH 4 ) SHeCaSDa (SF 6 ) TFMeCaSDa (CF 4 ) The Reims group hosts 2 databases on a dedicated server: ECaSDa (C 2 H 4 ) S&MPO (O 3 )

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 Relational database (simplified) schema Main ideas: Store states Transitions refer to upper and lower state IDs

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 MeCaSDa construction & languages Database developped from scratch. Database structure based on existing XSAMS schema (IAEA’s XML Schema for Atomic, Molecular and Solid data), adapted to requests. XSAMS was modified for specific methane requirements. Fortran programs for data calculation, extraction and SQL table loading. The database is re-created each time data are updated (non-interactive). MySQL database. Node software written in Python under Django framework. Used to make correspondance with the XSAMS schema. Some Python development was needed for data extraction by requests. FORTRAN

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 Query through the VAMDC portal Search into multiple databases

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 II. Methane, CH 4 MeCaSDa: Methane Calculated Spectroscopic Database

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 Direct access to MeCaSDa

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 Methane’s complex spectrum 12 CH 4 global fit 13

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 Present status of line-by-line analyses ( 12 CH 4 ) Polyad / Spectral regionPositionsIntensitiesProfiles 1 – Ground state 0–200 cm -1 (> 5.0  m) Complete analysis, J ≤ 24 Complete analysis Perturber: N 2 2 – Dyad 1000–1800 cm -1 (5.6–10.0  m) Complete analysis, J ≤ 23 Complete analysis, + some hot bands Perturbers: He et N 2 3 – Pentad 2200–3300 cm -1 (3.0–4.6  m) Complete analysis, J ≤ 18 Complete analysis (cold bands) Perturbers: He, Ar, N 2, O 2, CH 4 4 – Octad 3700–4800 cm -1 (2.0–2.7  m) Very good analysis, J ≤ 21 Very good analysis, (cold bands) Perturbers: N 2 5 – Tetradecad 5400–6300 cm -1 (1.6–1.9  m) Satisfying analysis, J ≤ 15 Satisfying analysis (cold bands) No calculation 6 – Icosad 6600–7700 cm -1 (1.3 – 1.5  m) Very partial analysis (3 band among 20) No analysisNo calculation Upper polyads > 7800 cm -1 (< 1.28  m) No analysis No calculation Windows (polyad far wings, all regions) No analysis No calculation

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 States and transitions in MeCaSDa 12 CH 4 / 13 CH 4 Vib. levelsVib. sublevelsMaximum JRovib. states P 0 – GS1125/25282/282 P 1 – Dyad2225/251408/1408 P 2 – Pentad5925/255352/5352 P 3 – Octad82622/ /3874 P 4 – Tetradecad146017/018900/0

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 Methane absorption lines in MeCaSDa

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 Methane Raman lines in MeCaSDa

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 III. Ethylene, C 2 H 4 ECaSDa: Ethylene Calculated Spectroscopic Database

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 Present status of analyses ν 4 /ν 7 /ν 10 /ν 12 tetrad: Global analysis To be published soon Positions & intensities 1.6 and 3 μm: Preliminary analysis

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 States and transitions in ECaSDa 12 C 2 H 4 Vib. levelsVib. sublevelsMaximum J Rovib. states Scheme 1 P 0 – GS P 1 – ν 4 /ν 7 /ν 10 /ν Scheme 2 P 0 – GS P 1 – ν P 2 – ν 9 /ν P 3 – ν 5 +ν 9 /ν 5 +ν

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 IV. Sulfur hexafluoride, SF 6 & Carbon tetrafluoride, CF 4 SHeCaSDa: Sulfur Hexafluoride Calculated Spectroscopic Database TFMeCaSDa: Tetra-Fluoro-Methane Calculated Spectroscopic Database

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 Present status of analyses for SF 6 SF 6 absolute intensities is a difficult problem At present, the database only contains ν 3 –ν 1, ν 3 –ν 2, ν 3, ν 4 and ν 4 +ν 6 –ν 6, ν 2 +ν 3, 3ν 3 Global fits of levels implying ν 1, ν 2, ν 3 their combinations and overtones are undeway Only 32 % of the molecules in the ground state at 293 K Need to analyze hot bands to correctly model atmospheric absorption

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 Present status and analyses for CF 4 RAMAN Boudon et al., J. Raman Spectrosc. 44, 731–738 (2013) 2ν 1 –ν 1 Global analysis INFRARED Boudon et al., Mol. Phys. 109, 2273– 2290 (2011) Global analysis This is in HITRAN Coriolis Collaboration with C. Maul Goal : Analyze all lower states in order to understand the hot bands in the ν 3 region (65 % of CF 4 in GS at room T).

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 States and transitions

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 V. Conclusions and perspectives

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 Future developments Spectroscopic analyses: Continue the global fit approach Hot methane (combustions, brown dwarfs, exoplanets, … ) Towards higher excited states of ethylene Hot bands of SF 6 and CF 4 Database improvements: We look for another optimized SQL engine PostgreSQL could be a solution

69 th International Symposium on Molecular Spectroscopy / Champaign-Urbana, Illinois, USA, June 16–20, 2014 The SMPCA Group in Dijon Molecular Spectroscopy, Collisional Processes and Applications