1. CDSD-4000: high-temperature spectroscopic CO 2 databank S.A. Tashkun, V.I. Perevalov Laboratory of Theoretical Spectroscopy, V.E. Zuev Institute of Atmospheric Optics, Russian Academy of Sciences, 1, Zuev square, 634021, Tomsk, RUSSIA The 11th HITRAN Database Conference June 16 – June 18, 2010

2. Motivation The exoplanet COROT-7b is close enough to its star that its "day-face" is hot enough to melt rock. ScienceDaily (Oct. 1, 2009) The 11th HITRAN Database Conference June 16 – June 18, 2010 Aerothermal modeling for Mars entry missions Exoplanents Industrial applications High-temperature lab spectra CO 2 ↔ (1-x)CO 2 + xCO +x/2*O 2 Does CO 2 exist at 4000 K ? T (K)CO 2 COO2O2 15001.0. 2000.986 0.0014.007 2500.876.124.062 3000.575.425.213 3500.261.739.370 4000.106.894.447 molar composition x [moles], p=1 atm www.engr.colostate.edu/~allan/thermo/page11/co2/CO2reaction.html S. Depraz et al, An experimental setup for IR gas radiative property measurements at temperatures up to 6000 K: Application to CO 2 and CO 2 -N 2 mixtures 2009 Proceedings of the ASME Summer Heat Transfer Conference 2009, HT2009, 1 pp. 363 - 370.

3. History R.B. Wattson, L.S. Rothman JMS 119, 83 (1986); JQSRT 48, 763 (1992): HITEMP, T ref =1000 K, I cut ~ 10 -27 cm/mol J.B. Pollack et al, Icarus 103, 1 (1993): HOT-CO2, T ref =750 K, I cut = 10 -30 cm/mol S.A. Tashkun et al, JQSRT 82, 165 (2003): CDSD-1000, T ref =1000 K, I cut = 10 -27 cm/mol S.A. Tashkun, V.I. Perevalov (2008): CDSD-296, CDSD- 1000, CDSD-Venus L.S. Rothman et al, JQSRT, (2010): CDSD-HITEMP, update and merge of CDSD-296, CDSD-Venus, CDSD-1000 ftp.iao.ru /pub/CDSD_HITEMP ftp.iao.ru The 11th HITRAN Database Conference June 16 – June 18, 2010

4. How CDSD is created Effective Hamiltonian model (Teffo, Perevalov) Effective dipole moment model (Teffo, Perevalov) Line broadening model (Bykov, Lavrientieva) Observed positions Observed intensities RITZ code: checking assignments and recalibration of data GIP code: Line by line fit of an effective operator parameters to observed data CDSD code: create a databank using given Tref and Icutoff CDSD databank The 11th HITRAN Database Conference June 16 – June 18, 2010 A. Campargue and coworkers 2005 – 2010 R.A. Toth and coworkers 2008

5. CDSD-4000 Tcalc = 4000 K, Intensity cutoff = 10 -27 cm/molecule @ Tcalc Four isotopologues: 12 C 16 O 2, 13 C 16 O 2, 16 O 12 C 18 O, 16 O 12 C 17 O Tref = 296 K, Number of entries: 628 324 454 Format of the databank: HITRAN-2008 isotopologueentriesv min v max s min s max e max cm -1 cm/mol cm -1 12 C 16 O 2 573 881 31622683107.3E-1093.5E-1843522 13 C 16 O 2 30 805 16840667972.9E-1053.7E-2041423 16 O 12 C 18 O18 282 39639451402.2E-0956.9E-2136359 16 O 12 C 17 O5 355 57445749766.1E-0851.3E-2131011 Distributive of CDSD-4000: 2770 ascii files sorted by frequency Size of the distributive: ~ 20 Gb in zipped format Databank location: Institute of Atmospheric Optics, HITEMP site ???, … The 11th HITRAN Database Conference June 16 – June 18, 2010 CDSD-4000 will be available via

6. CDSD ingredients 12 C 16 O 2 : Q our (4000) = 379231.; Q Osipov (4000) = 379960.; D = 43 869 cm -1 The 11th HITRAN Database Conference June 16 – June 18, 2010 Partition function: direct summation Linewidths and temperature exponents: g air, g self, n air, n self : a semi-empirical model V. M. Osipov, Mol Phys 102, 1785 (2004) A.D. Bykov, N.N. Lavrentieva, and L.N. Sinitsa, Proceedings of SPIE 4678, 29 (2002) Lineshifts : s air,: an empirical model J.-M. Hartmann, JQSRT 110, 2019 (2009) Enegry cutoff = 44000 cm -1

7. 4.3 μm region Fig 2. Experimental conditions: T = 2850 K, P = 2 atm, L = 2.34 cm 0.24 CO 2, 0.18 CO, 0.35 H 2 O, 0.09 O 2 Spectral slitwidth ~ 3cm -1 Simulation conditions: Icutoff = 10 -25 cm/molecule, Lorentz contour Wing length 2 cm -1 Apparatus function: triangle, 3cm -1 Dependence on Icutoff Icutoff = 10 -25 : 6.9*10 6 lines Icutoff = 10 -27 : 71.7*10 6 lines The 11th HITRAN Database Conference June 16 – June 18, 2010 C.C. Ferriso et al, JOSA 56, 171 (1966) T- dependence

8. 15μm region C.B. Ludwig et al, JOSA 56, 1685 (1966) Fig 4. Experimental conditions: T = 2300 K, P = 1 atm, L = 1.67 cm 0.49 CO 2 Spectral slitwidth ~ 5cm -1 Simulation conditions: Icutoff = 10 -25 cm/molecule Lorentz contour Wing length 2 cm -1 Apparatus function: triangle, 5 cm -1 The 11th HITRAN Database Conference June 16 – June 18, 2010 S.P. Bharadwaj, M.F. Modest JQSRT 103 146 (2007)

9. 2.7 μm region Etude expérimentale et modélisation des propriétés radiatives de mélanges gazeux de type CO 2 -N 2 à très haute température. Applications aux rentrées atmosphériques martiennes. Sébastien DEPRAZ (DEFA) Directeur s de thèse : Anouar SOUFIANI (EM2C) Marie-Yvonne PERRIN (EM2C) The 11th HITRAN Database Conference June 16 – June 18, 2010 Simulation with CDSD-1000 (green line) CDSD-4000 (black line)

10. Future work  Add less abundant isotopologues 16 O 13 C 18 O, …  Add pressure self-shifts  Efficient software for LBL calculations  Refitting models with new measurements (an endless loop …) The 11th HITRAN Database Conference June 16 – June 18, 2010 Acknowledgement A. Campargue L. Rothman I. Gordon L. Brown S.-M. Hu

11. Financial support The 11th HITRAN Database Conference June 16 – June 18, 2010 S.A. Tashkun acknowledges support from a joint RFBR (09-05- 92508-ИК_а) and CRDF (RUG1-2954-TO-09) grant. RFBR - CNRS grant 09-05-93105-НЦНИЛ_а.