Infrared spectroscopy of planetological molecules Isabelle Kleiner Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), Créteil, France.

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Infrared spectroscopy of planetological molecules Isabelle Kleiner Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), Créteil, France

Summary Planetary observations Strategy and methods Molecular systems: NH 3, PH 3, CH 3 CN, 13 CH 3 D

GOOD SPATIAL RESOLUTION -Orbiting Spacecraft : GALILEO: observations of Venus (1990) : 3 CO  m mission to Jupiter (1996), Probe : first in-situ observations ! NIMS : Near Infrared Mapping Spectrometer Grating spectrometer,  m R =  m 1  m

Planetary observations -Ground based observatories: Canada-France-Hawaii Telescope (CFHT)

Cassini/Huygens Study of Saturnian system, launched 1997 Flew past Jupiter on december 2000 Go into orbit of saturn in july 2004 ESA entry probe Huygens in Titan atmosphere 14/01/2005 -Visible and Infrared Mapping Spectrometer (VIMS)  m; visible  m; IR -Composite Infrared Spectrometer (CIRS) cm -1 Interferometers, Resolution 0.5 cm -1

Line shape parameters (Voigt) self-broadening coefficients, pressure brodening, line mixing… Basic transition line parameters: ● Line position (or center frequency) ● Line intensity at 296 K ● Lower state energy (for temperature dependence) ● Vibrational - rotational quantum assignment WHAT DO WE NEED FOR ANALYZING PLANETARY SPECTRA?

How to model the IR spectra of NH 3,PH 3, C 3 H 8 in the gas phase? STRATEGY USED 1)First step : obtain experimental data for both line positions and line intensities of pure 14 NH 3, PH 3, … in the lab. 2) Analyze the data using an appropriate theoretical approach : taking into account :- inversion motion of NH 3, - different interactions between energy levels for NH 3 and PH 3.  “ best ” energy and intensity parameters obtained  complete line-by-line prediction with all information needed.

NH 3 and PH 3 : Giant Planets -Largest planetary bodies in solar system (99.56% of the planetary mass) « Gas giants »: H 2 and He : Jupiter Saturn « ice giants » : ices of water and CH 4 : Uranus Neptune Mean temperatures at 1 bar : Jupiter: 167 K; Saturn: 138 K (Uranus:79K,Neptune : 70K)

3 microns spectral range: Saturn and Jupiter have very different spectra NH 3 ice cloud PH 3 : NEED FOR SPECTROSCOPIC DATA !

Phosphine is a molecule of astrophysical and astronomical interest and has been observed in both the Jupiter and Saturn atmospheres Between K: 4PH 3 + 6H 2 O P 4 O 6 +12H 2 At the cold temperatures of upper troposphere should not be detectable BUT vertical mixing transports PH 3 faster than oxidation. PH 3 abundance gives information on vertical circulation PH 3 : A non-equilibrium species

Development of the theoretical model and programs for fitting the IR spectra of C 3v molecules l l l 3 2 K-type interaction Diag Coriolis Fermi Coriolis l- type interaction Diag Coriolis Fermi Coriolis Fermi 2 42 l- type interaction Diag Coriolis Fermi Coriolis Fermi 1 K-type Interaction Diag Coriolis 3 l- type interaction Diag

Recent works on PH 3 - A computed room temperature line list for phosphine, Clara Sousa-Silva, Sergei N. Yurchenko, Jonathan Tennyson, J. Mol. Spectrosc. 288 (2013) using the TROVE program Spectroscopic parameters of phosphine, PH3, in its ground vibrational state, Holger S.P. Muller, JQSRT, 130, 335 (2013) Global calculations using potential functions and effective Hamiltonian models for vibration-rotation spectroscopy, V.Tuyterev, M. Rey, in preparation Line Positions and Intensities of the Phosphine (PH3) Pentad near 4.5 microns V. Malathy Devia, Isabelle Kleiner, Robert L. Sams, Linda R. Brown, D. Chris Benner, Leigh N. Fletcher, J. Mol. Spectrosc.,298, 11–23 (2014) -Line shape parameters of PH3 transitions in the pentad near 4-5 micron; self-broadened widths, line mixing and speed dependence, V. M. Devi, D. C. Benner, I. Kleiner, R. L. Sams and L. N. Fletcher, J. Mol. Spectrosc. 302, 17–33 (2014)

-The band 3 2 : -Low resolution of line positions (Maki et al. JCP 1973) - The octad bands: New line positions and intensities measurements ( Butler, Brown, Kleiner et al., JMS 2006) The Global analysis of the Dyad, pentad and octad bands: (Nikitin, Brown, Kleiner et al., JMS 2009) The 2 2 / /2 4 / 1 / 3 pentad: -Frequencies: rms=0.009 cm -1 up to J=16 (Tarrago et al. JMS, 1992, Ulenikov and al. JMS, 2002) -Intensities: rms= 13% (Tarrago et al. JMS, 1992 NEW MEASUREMENTS NEEDED The 2 / 4 dyad: -Frequencies: rms=0.0004cm -1 up to J=22 (Fusina and al, J.Mol.Struc.,2000 ) -Intensities: rms=2% (Brown, Kleiner and al., JMS, 2001) -Linewidth: self Broadening coefficients (J. Salem and al, JMS, 2004)