1. 1 Laurence S. Rothman Harvard-Smithsonian Center for Astrophysics Atomic and Molecular Physics Division Cambridge MA 02138, USA 60 th OSU Symposium on Molecular Spectroscopy Columbus OH 20-24 June 2005 New Edition of the HITRAN Spectroscopic Compilation

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

3. 3 HITRAN Line-by-line Parameters 160-character total Parameter Field size Definition Mol I2 Molecule number Iso I1 Isotopologue no.(1 = most abundant, 2 = second most abundant, …) ν if F12.6 Transition wavenumber in vacuum [cm -1 ] S if E10.3 Intensity [cm -1 /(molecule∙cm -2 ) @ 296K] A if E10.3 Einstein A-coefficient [s -1 ] γ air F5.4 Air-broadened half-width (HWHM) [cm -1 /atm @ 296K] γ self F5.4 Self-broadened half-width (HWHM) [cm -1 /atm @ 296K] E″ F10.4 Lower-state energy [cm -1 ] n air F4.2 Temperature-dependence coefficient of γ air δ air 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 ν if, S if, γ air, γ self, n air, δ air iref 6I2 Reference pointers for ν if, S if, γ air, γ self, n air, δ air * A1 Flag for line-coupling algorithm g′, g″ 2F7.1 Upper and Lower statistical weights

4. 4 Diatomics in HITRAN NO + (NO cation) N 2 (nitrogen) Bands Molecule ClO (chlorine monoxide) HI (hydrogen iodide) HBr (hydrogen bromide) HCl (hydrogen chloride) HF (hydrogen fluoride) OH (hydroxyl radical) NO (nitric oxide) 3 O 2 (oxygen) 0-0, 1-1, 1-0, 2-1, 2-0, 3-1, 3-0, 4-1 CO (carbon monoxide) # of Isotopo -logues 6 3 3 1 2 2 1 2 1 1 0-0, 1-1, 1-0, 2-1, 2-0, 3-0 1-0 0-0, 1-1, 1-0, 2-1, 2-0, 3-1, 3-0, 4-0 0-0, 1-1, 1-0, 2-1, 2-0, 3-1, 3-0, 4-1, 4-0 0-0, 1-0 0-0, 1-1, 1-0, 2-1, 2-0, 3-1, 3-0, 4-0, 5-0 1-0, 2-1, 3-2, 4-3, 5-4, 6-5

5. 5 Triatomics in HITRAN HOBr (hydrobromous acid) HO 2 (hydroperoxyl radical) H 2 S (hydrogen sulfide) HCN (hydrogen cyanide) HOCl (hypochlorous acid) OCS (carbonyl sulfide) NO 2 (nitrogen dioxide) Molecule SO 2 (sulfur dioxide) N 2 O (nitrous oxide) O 3 (ozone) CO 2 (carbon dioxide) H 2 O (water) Bands # of Isotopo -logues 6 8 5 1 2 5 2 1 5 2 3 3 156 bands, from 0 to 25232 cm -1 324 bands, from 442 to 12783 cm -1 92 bands, from 0 to 4061 cm -1 114 bands, from 0 to 7797 cm -1 8 bands, from 0 to 4093 cm -1 12 bands, from 0 to 3075 cm -1 51 bands, from 0 to 4119 cm -1 000-000, 001-001, ν 1, ν 3, from 1 to 3800 cm -1 18 bands, from 0 to 3424 cm -1 14 bands, from 2 to 4257 cm -1 000-000, ν 3, ν 2, ν 1, from 0 to 3676 cm -1 000-000, from 0 to 316 cm -1

6. 6 More Molecules in HITRAN COF 2 (carbonyl fluoride) PH 3 (phosphine) C 2 H 2 (acetylene) H 2 O 2 (hydrogen peroxide) H 2 CO (formaldehyde) NH 3 (ammonia) Tetratomics SF 6 (sulfur hexafluoride) C 2 H 6 (ethane) CH 3 OH (methanol) C 2 H 4 (ethylene) Big ones Pentatomics CH 4 (methane) HNO 3 (nitric acid) CH 3 Cl (methyl chloride) HCOOH (formic acid) ClONO 2 (chlorine nitrate)

7. 7 Major updates H 2 O: ν, S 0-800 cm -1 – calculations of L. Coudert et al 500-8000 cm -1 – observations of R.A. Toth 9250-9600, 11400-12895, 13184-25000 cm -1 – observations of Mérienne, Coheur, et al γ air, δ air – algorithm of D. Jacquemart et al CO 2 : ν, S Calculations of S. Tashkun et al 2-µm region – observations of C. Miller and L.R. Brown Many new high-resolution observations O 3 : ν, S 49 bands 600-2400 cm -1 – based on MIPAS database 14-µm region with associated hot bands – Wagner et al γ air, γ self, n air, δ air – fitting by M.A.H. Smith et al

8. 8 Major updates N 2 O: ν, S ν 2 – observations of J. Johns 10-µm region – observations of Daumont et al 500-7500 cm -1 – observations of R.A. Toth γ air, γ self, n air, δ air – polynomial fitting CO: S overtones – Brault et al; Sung and Varanasi γ air, γ self, n air, δ air – polynomial fitting CH 4 : ν, S 4800-9200 cm -1 – observations and analysis of L.R. Brown “Trace” species: NO, NO 2, HNO 3, OCS, HCN, H 2 S, HCOOH, CH 3 OH…

9. 9 SS2843: Arctic Occultation measured by ACE, late February 2004 (C. Boone and P. Bernath, U. Waterloo, private communication 2004) Consistency of Retrievals using three Different Bands

10. 10 Improvement of Consistency using HITRAN 2004

11. 11 Global Spectral Consistency Laboratory Intercomparison of Ozone Bands 10-µm band and UV 300-350nm (Huggins bands) B. Picquet-Varrault et al, J.Phys.Chem. A 109, 1008-14 (2005) Agreement ~ 1.5% with HITRAN2000 Difference ~5.5% with HITRAN2004 4.8-µm band and Visible 515-715nm (Chappuis band) D.G. Dufour et al, in preparation (2005) Difference ~3% with HITRAN2000 Agreement ~0.1% with HITRAN2004 Conclusions or Possible Explanations ► 4.8-µm and 10-µm band intensities are inconsistent ► Chappuis cross-sections are too low ► Huggins cross-sections are too high ► All bands have problems at this level of accuracy ► Further studies are required to resolve this issue!

12. 12 Summary of HITRAN 2004 HITRAN line-by-line portion ● 39 molecules, 93 isotopologues ● 1,734,469 transitions (274 Mbytes) HITRAN IR Cross-sections ● 30 molecules ● 860 temperature-temperature sets (153 Mbytes) http://cfa-www.harvard.edu/HITRAN

13. 13

14. 14 C 2 F 6 (CFC-116) CCl 4 CCl 3 F (CFC-11)

15. 15 CClF 3 (CFC-13) CCl 2 F 2 (CFC-12) CF 4 (CFC-14) SF 6

16. 16 CH 3 C(O)OONO 2 (PAN) CClF 2 CF 2 CHClF (HCFC-225cb)