1. Jonathan Tennyson Physics and Astronomy, University College London Columbus June 2013 Molecular line lists for exoplanets and other atmosheres Artist’s impression of HD189733b C. Carreau, ESA

2. 5 year project from May 2011 Provide data for all molecular transitions important for exoplanet atmospheres Methodology: first principles quantum mechanical calculations, informed by experiment J Tennyson and S.N. Yurchenko, MNRAS, 425, 21 (2012).

3. 3 Taken from Bill Borucki 2012: (nearly) every star has planets

4. Transit of Venus June 8 th 2004 June 5 th /6 th 2012 Next: 10 th December 2117

5. Radial velocity / Occultation Period = 3.52 days Mass = 0.69 ±0.05 M Jupiter Radius = 1.35 ±0.04 R Jupiter Density = 0.35 ±0.05 g/cm 3 HD 209458b

6. Beaulieu et al., 2007 Knutson et al., 2007 HD189733b: Primary transit with Spitzer

7. Tinetti et al., Nature, 448, 163 (2007) ‏ Water, different T-P Water line list: BT2 Barber et al., 2006

8. Confirmation of Water,methane and hazes! Beaulieu et al., 2007 Knutson et al., 2007 Swain et al., 2008 Pont et al., 2007 G. Tinetti (private communication, 2008)‏

9. Giovanna Tinetti, UCL So far discovered: Water H 2 O Methane CH 4 Carbon dioxide CO 2 Carbon monoxide CO On HD189733b with more to come HD189733b too hot for life HCCH / HCN degeneracy

10. 0.4 - 16  m R ~ 300 ESA M3 candidate mission Giovanna Tinetti (UCL) launch 2024? Exoplanet Characterisation Observatory Telescope Baffle V-groove Side Sunshield GaAs Solar Cells Detectors Service Module 1.5m Silicon Carbide Mirror

11. Frontier Problems in Exoplanet Characterization Non-equilibrium processes in exoplanet atmospheres (Stevenson et al. 2010; Madhusudhan & Seager 2011; Moses et al. 2013) CH 4, CO, NH 3 Constraints on thermal inversions in hot Jupiters (Fortney et al. 2008; Spiegel et al. 2009) TiO, VO, H 2 S C/O ratios and Carbon-rich atmospheres (Fortney et al. 2008; Spiegel et al. 2009) H 2 O, CO, HCN, CH 4, C 2 H 2,TiH, FeH Constraints on exoplanet formation conditions (Madhusudhan et al. 2011; Oberg et al. 2011) H 2 O, CO, CH 4 Atmospheres and interiors of super-Earths (Bean et al. 2011; Desert et al. 2011; Miller-Ricci Kempton et al. 2011 ) H 2 O, CO 2 Slide courtesy of N Madhusudhan (Yale)

12. Primordial (Metal-poor) Terrestrial Planets (Oxidising) Giant-Planets & Cool Stars (Reducing atmospheres) Already available H 2, LiH HeH +, H 3 + H 2 D + OH, CO 2, O 3, NO H 2 O, HDO, NH 3 H 2, CN, CH, CO, CO 2, TiO HCN/HNC, H 2 O, NH 3, ExoMolO 2, CH 4, SO 2, SO 3 HOOH, H 2 CO, HNO 3 CH 4, PH 3, C 2, C 3, HCCH, H 2 S, C 2 H 6, C 3 H 8, VO, O 2, AlO, MgO, CrH, MgH, FeH, CaH, AlH, SiH, TiH, NiH, BeH, YO Molecular line lists for exoplanet & other atmospheres Available from elsewhere Already calculated at UCL Will be calculated during the ExoMol project list of molecules www.exomol.com Full details: J. Tennyson and S.N. Yurchenko, MNRAS, 425, 21 (2012),

13. Why theory, not experiment?

14. Exoplanets

15. Absorption ( T =300K) spectrum of NH 3 : Accuracy Experiment Theory

16. Absorption ( T =300K) spectrum of NH 3 : Accuracy Experiment Theory

17. Absorption ( T =300K) spectrum of NH 3 : Accuracy

18. Theory

19. Completeness: Absorption of ammonia (T=300 K) Less than 30,000 NH 3 lines known experimentally: BYTe contains 1.1 billion lines, about 40,000 times as many! BYTe S.N. Yurchenko, R.J. Barber & J. Tennyson, Mon. Not. R. astr. Soc., 413, 1828 (2011)

20. Absorption spectra of 14 NH 3 : Temperature effect

21. Ab initio calculations DMSPES Variational calculations Rovibrational wavefunctions Rovibrational energies Intensities (Einstein A if ) Line list Refinement Method: Spectrum from the “first-principles”

22. Shayesteh et al 2007 MOLPRO Line list: MgH Potential energy curve Dipole moment curve Line list: 6690 lines, N max =60 Solve for the motion of the nuclei MOLPRO REFINED Ab initio: solve for motion of electrons B Yadin et al, MNRAS 425, 34 (2012) LEVEL 8.0 R. Le Roy, Waterloo, Canada

23. Line list (in progress): C 2 Solve for the motion of the nuclei New program duo Sergei Yurchenko Line list: being computed … Potential energyDipole moment MOLPRO T. W. Schmidt et al 2011 Istvan Szabo REFINED

24. Sakellaris, et al. J. Chem. Phys. 134, 234308 (2011) FeO Not being attempted !

25. Dipole moment LEVEL 8.0 DVR3D C3C3 Potential energy Ab initio 18 electrons Ground electronic state Solve for the motion of the nuclei Line list: Ab initio: solve for motion of electrons to be computed … CASSCF P. Jensen, C. McMichael Rohlfing, and J. Almlöf, 1992, J. Chem. Phys. 97, 3399.

26. Dipole moment TROVE: Yurchenko, Thiel, Jensen 300 K line list, Clara Sousa-Silva PH 3 Potential energy Tunneling motion neglected Solve for the motion of the nuclei Line list: T=300 K ~ 14 M transitons Hot: will be > billion TROVE HITRAN JPL Ab initio PES [CCSD(T)/aug-cc-pV(Q+d)Z] Refined using lab spectra R. I. Ovsyannikov et al. J. Chem. Phys 129, 044309 (2008). Ab initio: CCSD(T)/aug-cc-pVTZ S.N. Yurchenko et al. J. Mol. Spectrosc 239, 71 (2006). TROVE JPL HITRAN First principles Predictions of tunnelling being investigated

27. Dipole moment TROVE Yurchenko, Thiel, Jensen CH 4 9D surface 130 000 geometries Potential energy Ab initio 10 electrons Ground electronic state Three 9D surfaces 130 000 geometries Solve for the motion of the nuclei Line list: Billions of transitions MOLPRO CCSD(T)-f12/QZ MOLPRO CCSD(T)-f12/QZ Ab initio: solve for motion of electrons Sergei Yurchenko

28. Line list for warm Methane (T>600 K, J34 ) : line positions, Einstein coefficients, lower state energies, quantum numbers T=300K 212,000 lines 323,720,766 lines

29. Absorption of Methane (T=300 K) Albert et al., JCP 2008

30. Absorption of Methane (T=300 K) n Albert et al., JCP 2008 3

31. THz absorption of Methane (T=300 K)

32. Absorption spectra of CH 4 : Temperature effect

33. H 2 CO T = 296 K Ahmed Al-Refaie

34. 50,000 processor hours. Wavefunctions > 0.8 terabites 221,100 energy levels (all to J=50, E = 30,000 cm  )‏ 14,889 experimentally known 506 Million transitions (PS list has 308M) >100,000 experimentally known with intensities  Partition function 99.9915% of Vidler & Tennyson’s value at 3,000K BT2 linelist Barber et al, MNRAS 368, 1087 (2006). http://www.tampa.phys.ucl.ac.uk/ftp/astrodata/water/BT2/

35. Obs: A. Coppalle & P. Vervisch, JQSRT, 35, 121 (1986)‏ New edition of HITEMP: LS Rothman, IE Gordon, RJ Barber, H Dothe, RR Gamache, A Goldman, VI Perevalov, SA Tashkun + J Tennyson, JQSRT, 111, 2139 (2010).

36. BT2 linelist used to to detect/model water Nova-like V838 MonCometary coma Atmosphere of Venus Exoplanets (4 so far!) Brown and M-dwarfs

37. As well as..... Water concentrations in explosions Design of high-T gas sensors Remote detection of forest fires Imaging gas turbine engines Temperature profile in flames Atmospheric models

38. Primordial (Metal-poor) Terrestrial Planets (Oxidising) Giant-Planets & Cool Stars (Reducing atmospheres) Already available H 2, LiH HeH +, H 3 + H 2 D + OH, CO 2, O 3, NO H 2 O, HDO, NH 3 H 2, CN, CH, CO, CO 2, TiO HCN/HNC, H 2 O, NH 3, ExoMolO 2, CH 4, SO 2, SO 3 HOOH, H 2 CO, HNO 3 CH 4, PH 3, C 2, C 3, HCCH, H 2 S, C 2 H 6, C 3 H 8, VO, O 2, AlO, MgO, CrH, MgH, FeH, CaH, AlH, SiH, TiH, NiH, BeH, YO Molecular line lists for exoplanet & other atmospheres list of molecules www.exomol.com Full details: J. Tennyson and S.N. Yurchenko, MNRAS, 425, 21 (2012)

39. Primordial (Metal-poor) Terrestrial Planets (Oxidising) Giant-Planets & Cool Stars (Reducing atmospheres) Already available H 2, LiH HeH +, H 3 + H 2 D + OH, CO 2, O 3, NO H 2 O, HDO, NH 3 H 2, CN, CH, CO, CO 2, TiO HCN/HNC, H 2 O, NH 3, ExoMol In progress Requested O 2, CH 4, SO 2, SO 3 HOOH, H 2 CO, HNO 3 CH 4, PH 3, C 2, C 3, HCCH, H 2 S, C 2 H 4, C 2 H 6, VO, O 2, AlO, MgO, CrH, MgH, FeH, CaH, AlH, SiH, TiH, NiH, BeH, YO Molecular line lists for exoplanet & other atmospheres list of molecules www.exomol.com Full details: J. Tennyson and S.N. Yurchenko, MNRAS, 425, 21 (2012) NaH, HF, HCl SiO, CS, NaCl, KCl

40. H2SH2S HNO 3 C3C3 CrH cross sections AlO NiH VO CH 4 SO 3 HOOH PH 3 C2H4C2H4 CH 2 O MSc students: SiO, CS, NaCl, KCll Citizen scientist: AlH

41. H2SH2S HNO 3 C3C3 CrH cross sections AlO NiH VO CH 4 SO 3 HOOH PH 3 C2H4C2H4 CH 2 O www.exomol.com Ala’a Azzam Sergei Yurchenko Dan Underwood Oleg Polyansky Clara Sousa-Silva Anatoly Pavlyuchko Renia Diamantopoulou Christian Hill Maire Gorman Andrey Yachmenev Andrei Patrascu Lorenzo Lodi Ahmed Al-Refaie

42. www.worldscibooks.com/physics/7574.html About the first edition “The best book for anyone who is embarking on research in astronomical spectroscopy” Contemporary Physics (2006) Published 2011

43. Cool atmospheres : dominated by molecular absorption Brown Dwarfs M-dwarf The molecular opacity problem Exoplanets? M Dwarf Planet Marley & Leggett (2008)

44. Cool stars: T = 2000 – 4000 K Thermodynamics equilibrium, 3-body chemistry C and O combine rapidly to form CO. M-Dwarfs: Oxygen rich, n(O) > n(C)‏ H 2, H 2 O, TiO, ZrO, etc also grains at lower T C-stars: Carbon rich, n(C) > n(O) H 2, CH 4, HCN, C 3, HCCH, CS, C 2, CN, etc S-Dwarfs: n(O) = n(C) Rare. H 2, FeH, MgH, no polyatomics Also (primordeal) ‘metal-free’ stars H, H 2, He, H , H 3 + only at low T

45. Sub-stellar objects: CO less important L-Dwarfs: T ~ 1500 K H 2, H 2 O, CH 4 T-Dwarfs: T ~ 1000 K ‘methane stars’ Y-Dwarfs: T ~ 500 K ammonia signature Exoplanets: hot Jupiters super-Earths How common are these objects? Deuterium burning test using HDO? Burn D only No nuclear synthesis