Jonathan Tennyson Physics and Astronomy, University College London

1. Molecular line lists for exoplanets and other atmospheres Jonathan Tennyson Physics and Astronomy, University College London Emory October 2012 Artist’s impression of HD189733b C. Carreau, ESA

2. Spectrum of a hot star: black body-like

3. Infra red spectrum of an M-dwarf star

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

5. 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)‏ H2, H2O, TiO, ZrO, etc also grains at lower T C-stars: Carbon rich, n(C) > n(O) H2, CH4, HCN, C3, HCCH, CS, C2, CN, etc S-Dwarfs: n(O) = n(C) Rare. H2, FeH, MgH, no polyatomics Also (primordeal) ‘metal-free’ stars H, H2, He, H, H3+ only at low T

6. Sub-stellar objects: CO less important L-Dwarfs: T ~ 1500 K H2, H2O, CH4 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

7. 2012: (nearly) every star has planets Taken from Bill Borucki’s presentation

8. Transit of Venus June 8th 2004 June 5th/6th 2012

9. Radial velocity / Occultation HD 209458b Period = 3.52 days Mass = 0.69 ±0.05 MJupiter Radius = 1.35 ±0.04 RJupiter Density = 0.35 ±0.05 g/cm3

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

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

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

13. So far discovered:Water H2O Methane CH4 Carbon dioxide CO2 Carbon monoxide CO On HD189733b with more to come HCCH / HCN degeneracy Giovanna Tinetti, UCL HD189733b too hot for life

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

15. list of molecules Molecular line lists for exoplanet & other atmospheres Available from elsewhere Already calculated at UCL Will be calculated during the ExoMol project NaH, HF, HCl www.exomol.com Full details: J. Tennyson and S.N. Yurchenko, MNRAS, 425, 21 (2012)

16. Why theory, not experiment?

17. Exoplanets

18. Absorption (T=300K) spectrum of NH3: Accuracy Experiment Theory

19. Absorption (T=300K) spectrum of NH3: Accuracy Experiment Theory

20. Absorption (T=300K) spectrum of NH3: Accuracy

21. Absorption (T=300K) spectrum of NH3: Accuracy Theory

22. Completeness: Absorption of ammonia (T=300 K) BYTe Less than 30,000 NH3lines known experimentally: BYTe contains 1.1 billion lines, about 40,000 times as many!

23. Absorption spectra of 14NH3: Temperature effect

24. Method: Spectrum from the “first-principles” Ab initio calculations Refinement DMS PES Variational calculations Rovibrational wavefunctions Rovibrational energies Intensities (Einstein Aif) Line list

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

26. Line list (in progress): C2 IstvanSzabo Potential energy Dipole moment MOLPRO MOLPRO REFINED T. W. Schmidt et al 2011 Solve for the motion of the nuclei Line list: New program duo Sergei Yurchenko being computed …

27. 300 K line list, Clara Sousa-Silva PH3 Dipole moment Potential energy Ab initio: CCSD(T)/aug-cc-pVTZ Ab initio PES [CCSD(T)/aug-cc-pV(Q+d)Z] Refined using lab spectra First principles Predictions of tunnelling being investigated R. I. Ovsyannikov et al. J. Chem. Phys 129, 044309 (2008). Tunneling motion neglected S.N. Yurchenko et al. J. Mol. Spectrosc 239, 71 (2006). Solve for the motion of the nuclei TROVE Line list: TROVE: Yurchenko, Thiel, Jensen TROVE HITRAN JPL HITRAN JPL T=300 K ~ 14 M transitons Hot: will be > billion

28. CH4 Ab initio: solve for motion of electrons Dipole moment Potential energy Three 9D surfaces 130 000 geometries 9D surface 130 000 geometries Ab initio 10 electrons Ground electronic state MOLPRO CCSD(T)-f12/QZ MOLPRO CCSD(T)-f12/QZ Line list: Solve for the motion of the nuclei TROVE Yurchenko, Thiel, Jensen Sergei Yurchenko Billions of transitions

29. 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

30. CH4: Matrix diagonalization (Symmetry representation) Td(M) 1,000,000 elements E A1 A2 E …0 … F1 F1 1,000,000 elements F1 F2 …0 … F2 F2

31. CH4: Matrix diagonalization (Symmetry representation) Td(M) 1,000,000 elements gns= 5 A1 gns= 5 A2 E gns= 2 E …0 … F1 gns= 3 F1 1,000,000 elements F1 F2 gns= 3 …0 … F2 F2

32. Structure of the sub-matrix: DK=±2 factorization (J=8) Cs C2v C3v D3h C2h … … K=0 …0 … Td (M) K=1 K=2 K=3 K=4 K=5 K=6 K=7 …0 … K=8

33. Absorption of Methane (T=300 K)

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

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

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

37. Absorption spectra of CH4: Temperature effect

38. BT2 linelist Barber et al, MNRAS 368, 1087 (2006). http://www.tampa.phys.ucl.ac.uk/ftp/astrodata/water/BT2/ • 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

39. 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).

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

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

42. list of molecules Molecular line lists for exoplanet & other atmospheres NaH, HF, HCl www.exomol.com Full details: J. Tennyson and S.N. Yurchenko, MNRAS, 425, 21 (2012)

43. list of molecules Molecular line lists for exoplanet & other atmospheres NaH, HF, HCl SiO, CS, NaCl, KCl www.exomol.com Full details: J. Tennyson and S.N. Yurchenko, MNRAS, 425, 21 (2012)

44. www.exomol.com AlO cross sections NiH VO CrH YO HCN C3 H2S PH3 CH4 HOOH SO3 MSc students SiO, CS, NaCl, KCl + one Citizen scientist: AlH

45. www.exomol.com Andrei Patrascu Lorenzo Lodi Maire Gorman Renia Diamantopoulou Christian Hill AlO cross sections NiH VO CrH YO HCN C3 Bob Barber H2S PH3 Clara Sousa-Silva Ala’a Azzam CH4 HOOH SO3 Oleg Polyansky Sergei Yurchenko Dan Underwood MSc students SiO, CS, NaCl, KCl + one Citizen scientist: AlH

46. 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

47. Molecular line lists for exoplanet & other atmospheres Andrei atrascu Lorenzo Lodi Istvan Szabo Ala’a Azzam Clara Sousa Silva Oleg Polyansky Sergei Yurchenko Jonathan Tennyson BenjaminYadin Pierandrea Conti Thomas Veness SO3 Dan Underwood