Spectroscopy of complex organic molecules on Titan A. JOLLY

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1 Spectroscopy of complex organic molecules on Titan A. JOLLY

2 Outline of the talk New molecules on Titan? Expected molecules from laboratory experiment Results from the Huygens lander Infrared observation from CIRS-CASSINI Improvement in infrared spectroscopy Ultraviolet observation from UVIS-CASSINI Improvement in ultraviolet spectroscopy

3 Past IR observations of TITAN

4 Species Abundances Predominant species N CH , Hydrocarbons C 2 H , C 2 H 2 1, , C 3 H C 2 H C 3 H 4 (propyne) , C 4 H C 3 H 4 (allene) < 10-9 C 6 H C 6 H 2? Titan s atmosphere Nitriles HCN HC 3 N , CH 3 CN 1, C 2 N 2 some 10-9 C 4 N 2 solid HC 5 N? Oxygenated compounds CO 3, , CO , H 2 O

5 Titan s Atmospheric chemistry Long UV short UV CH 4 N 2 C 2 H 4 HCN C 2 H 2 CH 3 CN CH 3 CCH HC 3 N C 2 H 6 C 4 H 2 C 2 N 2 C 3 H 8 condensation sedimentatio n

6 Dust formation on TITAN and in the laboratory? Organic particles are easily formed in a N 2 /CH 4 plasma Caracteristics : molecules formed (all molecules detected on Titan and more) Refraction Index (compared to Titan s albedo) Chemical composition (C/N ratio) UV emission Spectroscopic analysis (radicals ; CN, NH, CH...)...

7 IR spectrum of a mixture produced by a N2/CH4 plasma discharge

8 Huygens Atmosphérique Entry:

9 Huygens GC-MS data

10

11

12 Cassini at Saturn since 1. July 2004

13 INMS

14

15 CIRS Observations of Titan : various latitudes

16 CIRS Observations of Titan : north to south ratio

17 CASSINI MISSION Composite InfraRed Spectrometer

18 C 6 H 2? TITAN Limb Observation (CIRS) T = 100 K C 4 H 2 HC 3 N HC 5 N? CO 2 HCN C 2 H 2 Obs Sim Flux C 3 H cm -1

19 HC 3 N in Titan. Hot bands? HC 3 N Titan North Limb (180 km)? cm -1

20 Infrared Spectra of HC 3 N (resolution : 0.5 cm -1 ) Exp G E IS A Absorbance Absorbance ν 5 Exp This work 0.2 ν 5 -> 2ν 5 (Π - Σ ) ν 5 -> 2ν 5 (Π - ) W avenumber (cm -1 )

21 Energy level diagram : HC 3 N Hot bands in HC 3 N 2ν 5 Σ + + Σ + +Σ + ν 5 +ν 6 ν 5 +2ν 7 Π+Φ 33 % of the population in the ground level at room T Σ + + Π+Φ 2ν 6 ν 6 +2ν 7 ν 5 +ν 7 Σ + +Σ + Σ + +Σ + ν 6 +ν 7 ν 5 Π Π ν 6 2ν 7 Σ + + ν 7 Π Ground Σ +

22 Fayt et al. (2000) 181 sublevels between 0 and 1750 cm calculation by Fayt experiment 1500 abs. coeff cm -1

23 Hot HC 3 N bands in Titan HC 3 N Fayt 300 K Fayt 100 K Titan North Limb (180 km)

24 More hot bands on Titan? YES CIRS LIMB Observation of Titan Simulation with 300 K C 4 H Flux C3H cm -1

25 C 4 H 2 simulation

26 First absolute intensity measurement for HC 5 N in the infrared (resolution : 0.5 cm -1 ) ν 7 80 Abs. Coeff. (cm -1.atm -1 ) ν 8 ν 8 +ν 11? ν 9 +ν 10? Wavenumber (cm -1 )

27 Comparison with theoretical results HC 5 N Absolute Intensities (atm -1 cm -2 ) at 296 K Mode Vibration Position (cm -1 ) This work (2005) Theoretical Results* ν 1 /ν 3 +ν 5 C-H str. (R) 3333 (P) a /362 b ν 2 C=C str. (R) 2257 (P) a /138 b ν 3 C=C str. (R) (P) a /22.5 b ν 7 bend a /318 c ν 8 bend a /55 c * converted from km/mol to atm -1.cm -2 a Scemama (2002) b Botschwina (1997) c Deguchi (1984), Uyemura (1986)

28 CASSINI UVIS Team, Science (2005)

29 Experimental study done at BESSY : Berlin Synchrotron Facility (GERMANY) April and July 2005 HC 3 N absorption spectra depending on the Temperature K 220 K 3000 relative intensity ,5 122,0 122,5 123,0 Wavelength (nm)

30 Cyanopolyynes spectra above 120 nm, HCN Absorption coefficient (cm -1.amagat -1 ) Wavelength (nm)

31 Cyanopolyynes spectra, HCN, HC3N.. Absorption coefficient (cm -1.amagat -1 ) HCN HC 3 N Wavelength (nm)

32 Cyanopolyynes spectra, HCN, HC3N, HC5N.. Absorption coefficient (cm -1.amagat -1 ) HCN HC3N HC5N Wavelength (nm)

33 New C4H2 spectra and UVIS occultation spectra

34 Simplified photochemical model : polymerisation Reactions with radicals H + CH C H + H HC N+ CH HC N+ H 2n n n+ 3 C 2(n 1) 2 Photodissociation : C 1 H + CN HC N+ H 2n 2 2n+ C H + hν C H+ H 2n 2 2n Photodissociation rates: Φ( λ) S( λ) τ ( z) σ ( λ,t ) J= Quantum yield λ0 0 φ Solar Flux (photons.cm -2.s -1 ) Optical depth Absorption cross Section HC N+ hν C N+ H 2n + 1 2n+ 1 ( ) ( ) τ ( z) λ. S λ. e. σ( λ, T). dλ

35 Solar spectrum in the absorption domain of hydrocarbons and nitriles Solar Spectrum 1E10 1E9 1E8 Flux photon/s/cm2 1E Wavelength (nm)

36 Predicted relative abondance of polyynes and cyanopolyynes on Titan 1 HCN C 2 H 2 Cyanopolyynes Polyynes Abondance relative HC 3 N C 4 H 2 C 6 H 2 1E-3 HC 5 N Nombre de Carbone

37 CRL 618 : Nebuleuse proto-planétaire riche en carbone

38 Predicted relative abondance of polyynes on Titan and CRL618 1 C 2 H 2 TITAN CRL 618 Abondance relative 0.1 C 4 H 2 C 6 H Nombre de Carbone

39 ISO Observation of CRL 618 Observations 1.1 Spectra calculation Transmission C 6 H 2 C 4 H 2 HCN C 6 H 2 /C 4 H 2 = 0.6 C 2 H Wavenumber (cm -1 )

40 Predicted relative abondance of cyanopolyynes on Titan and CRL618 1 HCN TITAN CRL 618 Abondance relative HC 3 N HC 5 N 1E Nombre de Carbone

41 1,2 1,1 ISO Observation of CRL618 Obs Sim 1,0 0,9 HC 5 N Flux 0,8 0,7 0,6 C 6 H 2 C 4 H 2 HC 3 N HCN 0,5 0,4 0,3 C 2 H cm -1

42 Titan's spectroscopic database The LISA Team and collaborators UV spectroscopy Titan's spectroscopic :Yves Benilan database, Thomas Ferradaz, Martin Schwell, Marie-Claire Gazeau, Nicolas Fray, Hans Jochims (Berlin) IR spectroscopy : Yves Benilan, Jean Claude Guillemin (Rennes), André Fayt (Louvain la neuve)

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