The HITRAN Database Laurence S Rothman Iouli E

The HITRAN Database Laurence S. Rothman Iouli E. Gordon Harvard-Smithsonian Center for Astrophysics Atomic and Molecular Physics Division Symposium on Laboratory Astrophysics at the Cf. A Cambridge, USA 20 September 2010 1

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Joseph-Marie Jacquard – 1801 Charles Babbage ~ 1820 HITRAN – 1973 Florida - 2000 5

Molecular Absorption Lambert-Beers Law of Absorption: Radiation Field Matter Coupling

Molecular Absorption Intensity in HITRAN database: (for HITRAN, Tref = 296 K) Partition Sum: Temperature dependence of halfwidth: air (pref, T) = air (pref, Tref) (Tref /T)n

HITRAN Line-by-line Parameters Parameter Field size Definition Mol I 2 Molecule number Iso I 1 Isotopologue no. (1 = most abundant, 2 = second most abundant, …) νif F 12. 6 Transition wavenumber in vacuum [cm-1] Sif E 10. 3 Intensity [cm-1/(molecule∙cm-2) @ 296 K] Aif E 10. 3 Einstein A-coefficient [s-1] γair F 5. 4 Air-broadened half-width (HWHM) [cm-1/atm @ 296 K] γself F 5. 4 Self-broadened half-width (HWHM) [cm-1/atm @ 296 K] E″ F 10. 4 Lower-state energy [cm-1] nair F 4. 2 Temperature-dependence coefficient of γair δair F 8. 6 Air pressure-induced shift [cm-1/atm @ 296 K] v′, v″ 2 A 15 Upper and Lower “global” quanta q′, q″ 2 A 15 Upper and Lower “local” quanta ierr 6 I 1 Uncertainty indices for νif , Sif , γair , γself , nair , δair iref 6 I 2 Reference pointers for νif , Sif , γair , γself , nair , δair * A 1 Flag for line-coupling algorithm 2 F 7. 1 Upper and Lower statistical weights g′, g″ 160 -character total 8

File Structure of HITRAN Compilation Level 1 Java. HAWKS Software Installers and Documentation HITRAN (line-transition parameters) IR Crosssections UV Aerosol Refractive Indices Level 2 Line-by -line Crosssections Line Coupling CO 2 data Global Data Files, Tables, and References Supplemental Alternate Moleculeby-molecule Level 3 9

Species Currently Covered (line-by-line portion) Molecule # of isotopologues H 2 O 6 HCl 2 COF 2 1 CO 2 8 HBr 2 SF 6 1 O 3 5 HI 1 H 2 S 3 N 2 O 5 Cl. O 2 HCOOH 1 CO 6 OCS 5 HO 2 1 CH 4 3 H 2 CO 3 O 1 O 2 3 HOCl 2 Cl. ON 2 O 2 NO 3 N 2 1 NO+ 1 SO 2 2 HCN 3 HOBr 2 NO 2 1 CH 3 Cl 2 C 2 H 4 2 NH 3 2 H 2 O 2 1 CH 3 OH 1 HNO 3 1 C 2 H 2 2 CH 3 Br 2 OH 3 C 2 H 6 1 CH 3 CN 1 HF 1 PH 3 1 CF 4 1 Molecule # of isotopologues 97 Isotopologues 10

Species Currently Covered (IR Cross-sections) Molecule Name SF 6 Sulfur hexafluoride CHCl. FCF 3 HCFC-124 Cl. ON 2 O Chlorine nitrate CH 3 CCl 2 F HCFC-141 b CCl 4 Carbon Tetrachloride CH 3 CCl. F 2 HCFC-142 b N 2 O 5 Dinitrogen pentoxide CHCl 2 CF 3 HCFC-225 ca HNO 4 Peroxynitric acid CCl. F 2 CHCl. F HCFC-225 cb C 2 F 6 CFC-116 CH 2 F 2 HFC-32 CCl 3 F CFC-11 CHF 2 CF 3 HFC-125 CCl 2 F 2 CFC-12 CHF 2 HFC-134 CCl. F 3 CFC-13 CFH 2 CF 3 HFC-134 a CF 4 CFC-14 CF 3 CH 3 HFC-143 a C 2 Cl 2 F 3 CFC-113 CH 3 CHF 2 HFC-152 a C 2 Cl 2 F 4 CFC-114 SF 5 CF 3 Trifluoromethyl sulfur pentafluoride C 2 Cl. F 5 CFC-115 CH 3 C(O)OONO 2 PAN CHCl 2 F HCFC-21 CH 3 CN Methyl cyanide CHCl. F 2 HCFC-22 C 6 H 6 Benzene CHCl 2 CF 3 HCFC-123 11

HITRAN evolution 1995 HITRAN law? HITEMP 2010 has 125 705 570 transitions!!!!!

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Methane Challenge 2. 3 μm new Global fit 1. 7 μm 14

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 15

IUPAC vs HITRAN Ro-vibrational levels for H 217 O 16

Some Sources of Errors in the HITRAN Database • Theory • Measurement – – – Calibration Resolution Photometric accuracy Pressure, temperature, stability, … Methods of analysis Identification of lines – – Perturbations Line shapes Lack of convergence Limit of basis sets • Units • Transcription 17

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 18

Access web site: http: //cfa. harvard. edu/HITRAN - Gives instructions for accessing compilation (free) - Updates - Documentation - Links to related databases - HITRAN facts - Related conferences 19

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Java. HAWKS Java version of HITRAN Atmospheric Wor. KStation KS • 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 21

HITRAN International Advisory Committee 22

SF 6 CF 4 (CFC-14) CCl. F 3 (CFC-13) CCl 2 F 2 (CFC-12) Typical Cross-section files 24

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