Spectroscopic Parameters Molecules in the atmospheres for the Atmospheres of Extrasolar Planets Laurence S. Rothman Harvard-Smithsonian Center for Astrophysics Atomic and Molecular Physics Division Cambridge MA 02138, USA Molecules in the atmospheres of extrasolar planets Paris, FRANCE 19-21 Novembre 2008 1

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- Planets lose energy by infrared radiation 1824 ► Greenhouse effect - gases in the atmosphere increase the surface temperature of the Earth - Planets lose energy by infrared radiation (that Fourier called "chaleur obscure" or "dark heat") - Fourier transform spectroscopy (FTS) Jean Baptiste Joseph Fourier March 21, 1768 – May 16, 1830 5

Joseph-Marie Jacquard – 1801 Charles Babbage ~ 1820 HITRAN – 1973 Florida - 2000 Babbage once contacted the poet Alfred Tennyson in response to his poem "The Vision of Sin". Babbage wrote, "In your otherwise beautiful poem, one verse reads, Every moment dies a man, Every moment one is born. ... If this were true, the population of the world would be at a standstill. In truth, the rate of birth is slightly in excess of that of death. I would suggest [that the next version of your poem should read]: Every moment 1 1/16 is born. Strictly speaking, the actual figure is so long I cannot get it into a line, but I believe the figure 1 1/16 will be sufficiently accurate for poetry." 6

HITRAN law? Like Moore’s law (number of transistors on a printed circuit doubles every 2 years). Moore’s law is a violation of Murphy’s law… HITRAN gets better and better. 7

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96 (2005) 139-204 9

(line-transition parameters) Global Data Files, Tables, and References File Structure of HITRAN Compilation JavaHAWKS Software Installers and Documentation Level 1 Level 2 HITRAN (line-transition parameters) IR Cross-sections UV Aerosol Refractive Indices Line Coupling CO2 data Global Data Files, Tables, and References Line-by-line Cross-sections Level 3 Supplemental Supplemental Alternate Molecule- by-molecule 10

HITRAN Line-by-line Parameters Field size Definition Mol I2 Molecule number Iso I1 Isotopologue no.(1 = most abundant, 2 = second most abundant, …) νif F12.6 Transition wavenumber in vacuum [cm-1] Sif E10.3 Intensity [cm-1/(molecule∙cm-2) @ 296K] Aif E10.3 Einstein A-coefficient [s-1] γair F5.4 Air-broadened half-width (HWHM) [cm-1/atm @ 296K] γself F5.4 Self-broadened half-width (HWHM) [cm-1/atm @ 296K] E″ F10.4 Lower-state energy [cm-1] nair F4.2 Temperature-dependence coefficient of γair δair F8.6 Air pressure-induced shift [cm-1/atm @ 296K] v′, v″ 2A15 Upper and Lower “global” quanta q′, q″ 2A15 Upper and Lower “local” quanta ierr 6I1 Uncertainty indices for νif , Sif , γair , γself , nair , δair iref 6I2 Reference pointers for νif , Sif , γair , γself , nair , δair * A1 Flag for line-coupling algorithm g′, g″ 2F7.1 Upper and Lower statistical weights 160-character total 11

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Some New Updates H2O – water CO2 – carbon dioxide CH4 – methane ►Reassignment of visible spectra [Tennyson et al] ► Update of γself [Gamache et al] ► Implement IUPAC results [Tennyson et al] CO2 – carbon dioxide ► OCO line list for near IR [Brown, Miller et al] ► CDSD [Tashkun et al] ► Weak bands [Campargue et al] ► New 0 to 4800 cm-1 [Brown et al] ► CH3D 3300-3700 cm-1 [Brown et al] ► Line-shape calculations, supplemented with exp. CH4 – methane 13

Methane Challenge  Global fit  1.7 μm 2.3 μm new 14

More New Updates….. O3 – ozone O3 – ozone O3 – ozone O3 – ozone ► Major update 1632-5870 cm-1 [Reims/Tomsk] ► Improved line-shape algorithm O2 – Oxygen ► (UV) Corrected Schumann-Runge list ► Added Herzberg bands ► Improved A-band [Brown and co-workers] HNO3 – nitric acid ► Update 600-1790 cm-1 [Perrin et al] ► Further Improvements in 11-µm region [Gomez et al] 15 O3 – ozone O3 – ozone O3 – ozone A major update has been made for the first three isotopologues of ozone, thanks to the Reims-Tomsk collaborative effort [http://smpo.iao.ru]. The new data cover bands in the spectral range 1632 to 5870 cm-1, thereby extending the short wavelength coverage of HITRAN. In addition, an improved algorithm for incorporating ozone line-shape parameters has been applied to all ozone bands in the compilation. O3 – ozone A major update has been made for the first three isotopologues of ozone, thanks to the Reims-Tomsk collaborative effort [http://smpo.iao.ru]. The new data cover bands in the spectral range 1632 to 5870 cm-1, thereby extending the short wavelength coverage of HITRAN. In addition, an improved algorithm for incorporating ozone line-shape parameters has been applied to all ozone bands in the compilation. A major update has been made for the first three isotopologues of ozone, thanks to the Reims-Tomsk collaborative effort [http://smpo.iao.ru]. The new data cover bands in the spectral range 1632 to 5870 cm-1, thereby extending the short wavelength coverage of HITRAN. In addition, an improved algorithm for incorporating ozone line-shape parameters has been applied to all ozone bands in the compilation. A major update has been made for the first three isotopologues of ozone, thanks to the Reims-Tomsk collaborative effort [http://smpo.iao.ru]. The new data cover bands in the spectral range 1632 to 5870 cm-1, thereby extending the short wavelength coverage of HITRAN. In addition, an improved algorithm for incorporating ozone line-shape parameters has been applied to all ozone bands in the compilation.

Species Currently Covered (line-by-line portion) Molecule # of isotopo-logues H2O 6 HCl 2 COF2 1 CO2 8 HBr SF6 O3 5 HI H2S 3 N2O ClO HCOOH CO OCS HO2 CH4 H2CO O O2 HOCl ClON2O NO N2 NO+ SO2 HCN HOBr NO2 CH3Cl C2H4 NH3 H2O2 CH3OH HNO3 C2H2 CH3Br OH C2H6 CH3CN HF PH3 CF4 97 Isotopologues 16

Species Currently Covered (IR Cross-sections) Molecule Name SF6 Sulfur hexafluoride CHClFCF3 HCFC-124 ClON2O Chlorine nitrate CH3CCl2F HCFC-141b CCl4 Carbon Tetrachloride CH3CClF2 HCFC-142b N2O5 Dinitrogen pentoxide CHCl2CF2CF3 HCFC-225ca HNO4 Peroxynitric acid CClF2CF2CHClF HCFC-225cb C2F6 CFC-116 CH2F2 HFC-32 CCl3F CFC-11 CHF2CF3 HFC-125 CCl2F2 CFC-12 CHF2CHF2 HFC-134 CClF3 CFC-13 CFH2CF3 HFC-134a CF4 CFC-14 CF3CH3 HFC-143a C2Cl2F3 CFC-113 CH3CHF2 HFC-152a C2Cl2F4 CFC-114 SF5CF3 Trifluoromethyl sulfur pentafluoride C2ClF5 CFC-115 CH3C(O)OONO2 PAN CHCl2F HCFC-21 CH3CN Methyl cyanide CHClF2 HCFC-22 C6H6 Benzene CHCl2CF3 HCFC-123 17

IUPAC Water-Vapor Task Distributed Information System Collect all kinds of original information about the high-resolution spectroscopy of the water molecule Provide active storage of these data and related metadata Deliver information to users in different forms via the Internet 18

Ro-vibrational levels IUPAC vs HITRAN Ro-vibrational levels for H217O 19

Intersection des Banques de Données HITRAN et HITEMP 20

HITRAN vs HITEMP CO2 250 ppm CO2 5-meter source 100 feet above the surface 21

Figure 4. Comparison of CDSD and old HITEMP with measurments at 1550K Comparison of CDSD and old HITEMP with Measurements 22

HITEMP Line-absorption parameters in HITRAN format Constituents - Water Vapor: 0 to 25000 cm-1 @ 1000K,1500K - Carbon Dioxide: 400 to 10000 cm-1 @ 1000K - Carbon Monoxide: 0 to 10000 cm-1 @ solar temperature - Hydroxyl Radical: 0 to 19300 cm-1 @NLTE 23

New HITEMP Water List Assembly List created using BT2 database - for principal isotopologue, created at 296K with lines that have significant intensity at 4000K, J <50 Partition Function Experimental high-temperature line positions - Based on quantum numbers, replace frequencies with experimental ones (when available) HITRAN database Convert to HITRAN2004 format Combination of BT2, high-temperature experiments, and HITRAN Einstein A-coefficients, Statistical weights Line-shape parameters (widths, shifts, etc) HITEMP Water Line List 24

Improvements and Enhancements to the Compilation being considered ►More temperature-pressure sets of cross-sections (IR and UV) ►Improved database structure (IUPAC paradigm) ►High-temperature parameters (HITEMP) ►Molecules for astrophysics applications ►Refined line-shape parameters ►Additional line-mixing algorithms ►Collision-Induced Absorption bands 25

Access web site: http://cfa.harvard.edu/HITRAN Gives instructions for accessing compilation (free) Updates - Documentation - Links to related databases - HITRAN facts - Related conferences 26

JavaHAWKS Java version of HITRAN Atmospheric WorKStation Functions to manipulate and filter the HITRAN and associated molecular spectroscopic databases Plotting of line-by-line files and cross-section files Internet access to HITRAN and other related databases Links to abstracts that are the sources for HITRAN parameters Access to archival HITRAN documentation 27

Some Sources of Errors in the HITRAN Database Measurement Calibration Resolution Photometric accuracy Pressure, temperature, stability, … Methods of analysis Identification of lines Theory Perturbations Line shapes Lack of convergence Limit of basis sets Units Transcription 28

HITRAN International Advisory Committee 29

Typical Cross-section files (CFC-12) CCl2F2 (CFC-13) CClF3 (CFC-14) CF4 SF6 30

Figure 1. Comparison of different theoretical line lists with high-temperature experiments with high-temperature observation 31