1. Preliminary modeling of CH 3 D from 4000 to 4550 cm -1 A.V. Nikitin 1, L. R. Brown 2, K. Sung 2, M. Rey 3, Vl. G. Tyuterev 3, M. A. H. Smith 4, and A.W. Mantz 5 1. Laboratory of Theoretical Spectroscopy, V.E. Zuev Institute of Atmospheric Optics, SB RAS, Academician Zuev square, 634021, Tomsk, Russia 2. Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, CA 91109, USA 3. Groupe de Spectrométrie Moléculaire et Atmosphérique, UMR CNRS 7331, Université de Reims, 4. U.F.R. Sciences, B.P. 1039, 51687 Reims Cedex 2, France 4. Science Directorate, NASA Langley Research Center, Hampton, VA 23681, USA 5. Dept. of Physics, Astronomy and Geophysics, Connecticut College, 270 Mohegan Avenue, New London, CT 06320, USA 1 Molecular Spectroscopy Symposium June 2012 RB-07

2. CH 3 D Vibrational States: Polyads 2 Molecular Spectroscopy Symposium June 2012 RB-07 a) Enneadecad: 19 overtone & combination bands b) Nonad: 3 fundamentals 6 (overtone & combo) c) Triad: 3 fundamentals a) Nikitin et al. 2006 b) Nikitin et al. 2002 c) Nikitin et al. 1997 Focus of this study Upper part = Polyad3 12 bands, 23 sub-vibs

3. The Enneadecad Polyad of CH 3 D 3 Molecular Spectroscopy Symposium June 2012 RB-07 Prior Ennea work Nikitin 2006 3250 – 3700 cm -1 for outer planets Predicted upper state levels by extrapolating ro-vibrational constants from Triad and Nonad. Ulenikov et al. 2010 (assigned positions to 33 Ennea sub-vibs) using cold data from Zurich (ETH) FTS

4. Modeling CH 3 D Ennea Intensities 4 Molecular Spectroscopy Symposium June 2012 RB-07 Lower Ennea: Nikitin et al. 2006 measured and modeled 874 intensities of 6 bands New goal: Measure more intensities and provide initial prediction for the Upper Ennea (Polyad3)

5. CH 3 D Experimental Spectra 5 Molecular Spectroscopy Symposium June 2012 RB-07

6. CH 3 D at 291 K and 80 K 6 Molecular Spectroscopy Symposium June 2012 RB-07 Kitt Peak FTS 2.4 m and 4.88 torr at 291 K Used for Nonad (2002) and lower Enneadecad (2006) Positions and intensities retrieved by Nikitin et al. withTomsk software JPL Bruker 0.204 m and 3.35 torr at 80 K Positions and intensities retrieved by Brown with JPL software

7. CH 3 D: retrieve line intensities one spectrum at a time 7 Molecular Spectroscopy Symposium June 2012 RB-07 Q branch of ν 3 + ν 4 at 4313 cm -1 (T=80 K) Top panel: observed – synthetic spectra Lower panel: Red: synthetic Black: observed In total over 4000 features measured at 80 K by non-linear least squares

8. Assigning CH 3 D Quantum Numbers 8 Molecular Spectroscopy Symposium June 2012 RB-07 4074 cm-1 4077 Tomsk analysis software: retrieves positions & intensities, and finds quantum assignments by combination differences

9. Average CH 3 D intensities: (80 K JPL) + (291 K Tomsk) 9 Molecular Spectroscopy Symposium June 2012 RB-07 Obs Pos quanta a E" E' obs ( +E") S obs (296K) Averaged cm -1 J” C” α” J’ C’ α’ cm -1 cm -1 cm/molecule %rms =============================================================================== 4050.931106 2 E 1 1 E 28 24.649117 4075.580223 5.343E-23. 4066.449698 1 E 1 1 E 28 9.130579 4075.580277 7.056E-23. 4103.031972 2 A1 1 1 A2 19 23.279194 4126.311166 6.512E-23. 4126.311111 0 A1 1 1 A2 19 0.000000 4126.311292 1.861E-22 2.1 4112.752281 6 E 1 5 E 127 164.240493 4276.992774 5.302E-23 0.3 4126.414250 5 E 4 5 E 127 150.578239 4276.992489 7.671E-23 2.0 4193.936614 4 E 2 5 E 127 83.056222 4276.992836 9.333E-23 3.6 4079.934893 6 E 4 5 E 127 197.057437 4276.992450 3.024E-22 0.5 4145.772883 7 A1 1 7 A2 87 229.404232 4375.177115 1.143E-22. 4096.075326 8 A1 1 7 A2 87 279.101330 4375.177512 6.068E-23 1.9 4212.302061 6 A1 1 7 A2 87 162.875088 4375.177363 7.902E-23 2.0 4156.055376 9 E 2 9 E 213 354.230581 4510.286206 9.970E-23 0.2 4225.737777 8 E 2 9 E 213 284.548935 4510.286235 3.884E-23 2.9 4229.823556 8 E 1 9 E 213 280.462997 4510.286418 9.407E-23 1.8 4167.196358 13 A2 1 14 A1 115 704.460648 4871.657006 8.776E-23. 4155.126082 13 E 3 14 E 232 726.049202 4881.175284 6.513E-23.

10. 1308 selected CH 3 D Intensities: ( in units of cm/molecule at 296 K) 10 Molecular Spectroscopy Symposium June 2012 RB-07 (2v 5 +v 6 ) (2v 3 +v 5 ) (v 1 + v 6 ) (v 4 + v 6 ) ( (v 3 + 2v 5 ) (v 3 + v 4 ) (2v 2 ) (2v 2 ) (3v 5 ) (v 1 +v 5 ) (v 4 + v 5 ) (v 2 +2v 6 )

11. 11 Molecular Spectroscopy Symposium June 2012 RB-07 CH 3 D Vibrational sublevels Center obs (cm -1 ) Number of fitted positions St. Dev (10 -3 cm -1 ) # fitted intensitiesSt.Dev (%) 2v 5 +v 6 1E 4058.692883991.05215 7.3 2v3+v5 E2v3+v5 E 4067.854252516.7083 8.8 2v 5 +v 6 A 1 4081.328981147.5721 12.7 2v 5 +v 6 A 2 487.7511 12.3 2v 5 +v 6 2E 4102.438801757.3941 11.5 v 1 +v 6 E 4122.589292901.08155 9.1 v 4 +v 6 A 1 4163.491002375.5590 9.3 v 4 +v 6 E 4170.359594396.11201 6.7 v 4 +v 6 A 2 1096.7328 9.2 v 3 +2v 5 A 1 4215.284291048.8932 8.1 v 3 +2v 5 E 4241.744121906.539 14.2 v 1 +v 3 A 1 00 v 3 + v 4 E 4313.424773879.08161 7.8 2v 2 A 1 4344.124591784.9385 6.8 3v 5 E 4356.886141807.137 25.4 3v 5 A 2 00 3v 5 A 1 4404.35936258.521 6.6 v 1 +v 5 E 4439.730172538.6844 13.3 v 4 +v 5 A 2 1041.5414 19.0 v 4 +v 5 E 4472.648493527.73140 10.5 v 2 +2v 6 A 1 346.934 14.6 v 4 +v 5 A 1 4484.823161316.3113 14.3 v 2 +2v 6 E 4486.88302 859.167 14.9

12. ∑ Line Intensities: 11 CH 3 D bands 12 Molecular Spectroscopy Symposium June 2012 RB-07 Vibrational Bands ∑ intensities calc at 296 K #dipoles (  =0) Interactions (  =1) # lines fitted 2v 3 +v 5 E 2.1 E-2010 83 2v 5 +v 6 A 1, A 2, 1E, 2E 13.0 E-2032288 v 1 + v 6 E 7.8 E-2011155 v 4 + v 6 A 1, A 2, E 12.0 E-2025319 v 3 +2v 5 A 1, E 1.1 E-2024 41 v 3 + v 4 E 5.9 E-2012 161 2v 2 2v 2 A 1 1.5 E-2010 85 3v 5 A 1, A 2, E 0.7 E-2010 8 v 1 +v 5 E 1.7 E-2012 44 v 4 +v 5 A 1, A 2, E 8.6 E-2023167 v 2 +2v 6 v 2 +2v 6 A 1, E 0.6 E-2010 11

13. Measured (top) & Calc. (bottom) CH 3 D Log (intensity) vs. cm -1 13 Molecular Spectroscopy Symposium June 2012 RB-07 4000 cm -1 4550

14. Preliminary modeling of CH 3 D 14 Molecular Spectroscopy Symposium June 2012 RB-07

15. Modeling the CH 3 D Enneadecad 15 Molecular Spectroscopy Symposium June 2012 RB-07 ► This work has been submitted to JQSRT with a supplemental linelist of ~4000 measured positions, intensities and known quantum assignments. More to come : HITRAN/ASA ► New measurements and analyses of line positions and intensities of CH 3 D in the infrared A. Nikitin 1, L. Brown 2, K. Sung 2, M. A. Smith 4, A. Mantz 5 X. Thomas 3, L. Regalia 3, L. Daumont 3, R. Kochanov 3,1, M. Rey 3, V. Tyuterev 3, In order to extend the knowledge of 12 CH 3 D weak lines, new long path FTS measurements are recorded in Reims between 1850 and 9200 cm -1 at 290 K, 2.58 Torr with path lengths of 201, 302 and 1603 m. In this work we focus particularly on the full spectral range of this polyad (3300-4550 cm -1 ). The aim is to complete the previous study [1] by intensity measurements of lines corresponding to higher J transitions and to improve the modelling in the 3300-4700 cm -1 range using new theoretical predictions for band centers and resonance coupling parameters.

16. Acknowledgements: This work is supported by 16 Molecular Spectroscopy Symposium June 2012 RB-07 ► The ANR project “CH4@Titan” (ref: BLAN08-2_321467). ► Groupement de Recherche International SAMIA between CNRS (France), RFBR (Russia) and CAS (China). ► IDRIS computer centre of CNRS France and of the computer centre Reims- Champagne-Ardenne. ► LEFE-CHAT INSU project APOA1 (CNRS, France). ► Program Number 22 ‘‘The fundamental problems of investigation and exploration of the Solar System’’ of Russian academia of science. ► Part of the research at the Jet Propulsion Laboratory, California Institute of Technology, the NASA Langley Research Center and Connecticut College was performed under contracts /grants with the National Aeronautics and Space Administration. A. Nikitin. thanks the ICM@MG SB RAS (Novosibirsk) and SKIF Siberia (Tomsk).