1 Laurence S. Rothman Harvard-Smithsonian Center for Astrophysics Atomic and Molecular Physics Division…

1

Laurence S. RothmanLaurence S. RothmanHarvard-Smithsonian Center for Astrophysics

Atomic and Molecular Physics DivisionCambridge MA 02138, USA

6060thth OSU Symposium on OSU Symposium onMolecular SpectroscopyMolecular Spectroscopy

Columbus OHColumbus OH20-24 June 200520-24 June 2005

New Edition of the HITRANNew Edition of the HITRANSpectroscopic CompilationSpectroscopic Compilation

2Level 3

Level 2

JavaHAWKS Software Installers and DocumentationLevel 1

File Structure of HITRAN CompilationFile Structure of HITRAN Compilation

Line-by-line

Molecule-by-molecule

Global Data Files, Tables,

and References

SupplementalSupplemental

Cross-sections

Alternate

HITRAN(line-transition

parameters)

IRCross-

sections

AerosolRefractive

Indices

LineCoupling

CO2 data

UV

3

HITRAN Line-by-line ParametersHITRAN Line-by-line Parameters

160-character total160-character total

ParameterParameter Field sizeField size DefinitionDefinitionMol I2 Molecule numberIso 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” quantaq′, q″ 2A15 Upper and Lower “local” quantaierr 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 algorithmg′, g″ 2F7.1 Upper and Lower statistical weights

4

Diatomics in HITRANDiatomics in HITRAN

NO+ (NO cation)

N2 (nitrogen)

BandsMolecule

ClO (chlorine monoxide)

HI(hydrogen iodide)

HBr(hydrogen bromide)

HCl(hydrogen chloride)

HF(hydrogen fluoride)

OH (hydroxyl radical)

NO (nitric oxide)

3O2 (oxygen)

0-0, 1-1, 1-0, 2-1, 2-0, 3-1, 3-0, 4-1CO(carbon monoxide)

# of Isotopo-logues

6

1 3g ga X 3 3

g gX X 1 3g gb X

3 2 2i iX X 0,1,2,3v 0,1,2,.....v

3 2 2i iX X 0,1,2,3v 0,1,2,.....v

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

2 2i iX X 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

Triatomics in HITRANTriatomics in HITRAN

HOBr (hydrobromous acid)

HO2 (hydroperoxyl radical)

H2S (hydrogen sulfide)

HCN (hydrogen cyanide)

HOCl (hypochlorous acid)

OCS (carbonyl sulfide)

NO2 (nitrogen dioxide)

Molecule

SO2 (sulfur dioxide)

N2O (nitrous oxide)

O3 (ozone)

CO2 (carbon dioxide)

H2O (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






000-000, 001-001, ν1, ν3, from 1 to 3800 cm-1



000-000, ν3, ν2, ν1, from 0 to 3676 cm-1

000-000, from 0 to 316 cm-1

6

More Molecules in HITRANMore Molecules in HITRAN

COF2

(carbonyl fluoride)

PH3

(phosphine)

C2H2

(acetylene)

H2O2

(hydrogen peroxide)

H2CO(formaldehyde)

NH3

(ammonia)

Tetratomics

SF6

(sulfur hexafluoride)

C2H6

(ethane)

CH3OH(methanol)

C2H4

(ethylene)

Big onesPentatomicsCH4

(methane)

HNO3

(nitric acid)

CH3Cl

(methyl chloride)

HCOOH(formic acid)

ClONO2

(chlorine nitrate)

7

Major updatesMajor updatesH2O: 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 γair , δair – algorithm of D. Jacquemart et al

CO2: ν, S• Calculations of S. Tashkun et al• 2-µm region – observations of C. Miller and L.R. Brown• Many new high-resolution observations

O3: ν, S• 49 bands 600-2400 cm-1 – based on MIPAS database• 14-µm region with associated hot bands – Wagner et al γair , γself , nair , δair – fitting by M.A.H. Smith et al

8

Major updatesMajor updatesN2O: ν, S• ν2 – observations of J. Johns• 10-µm region – observations of Daumont et al• 500-7500 cm-1 – observations of R.A. Toth γair , γself , nair , δair – polynomial fitting

CO: S• overtones – Brault et al; Sung and Varanasi γair , γself , nair , δair – polynomial fitting

CH4: ν, S• 4800-9200 cm-1 – observations and analysis of L.R. Brown

“Trace” species: NO, NO2, HNO3, OCS, HCN, H2S, HCOOH, CH3OH…

9

SS2843, HNO3 Retrieved from three different bands, HITRAN 2000

0

10

20

30

40

0 5 10 15volume mixing ratio (ppb by volume)

altit

ude

(km

)

870 cm-11330 cm-11700 cm-1

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 BandsConsistency of Retrievals using three Different Bands

10

SS2843, HNO3 Retrieved from three different bands, HITRAN 2004

05

10152025303540

0 5 10 15volume mixing ratio (ppb by volume)

altit

ude

(km

)

870 cm-11330 cm-11700 cm-1

Improvement of Consistency using HITRAN 2004Improvement of Consistency using HITRAN 2004

11

Global Spectral ConsistencyGlobal Spectral ConsistencyLaboratory Intercomparison of Ozone BandsLaboratory Intercomparison of Ozone Bands

10-10-µm band and UV 300-350nm (Huggins bands)µm band and UV 300-350nm (Huggins bands)B. Picquet-Varrault et al, B. Picquet-Varrault et al, J.Phys.Chem.J.Phys.Chem. A 109, A 109, 1008-141008-14 (2005) (2005)

Agreement ~ 1.5% with HITRAN2000Agreement ~ 1.5% with HITRAN2000Difference ~5.5% with HITRAN2004Difference ~5.5% with HITRAN2004

4.8-4.8-µm band and Visible 515-715nm (Chappuis band)µm band and Visible 515-715nm (Chappuis band)D.G. Dufour et al, D.G. Dufour et al, in preparationin preparation (2005) (2005)

Difference ~3% with HITRAN2000Difference ~3% with HITRAN2000Agreement ~0.1% with HITRAN2004Agreement ~0.1% with HITRAN2004

Conclusions or Possible ExplanationsConclusions or Possible Explanations► ► 4.8-4.8-µm and µm and 10-10-µm band intensities are inconsistentµm band intensities are inconsistent

► ► Chappuis cross-sections are too lowChappuis cross-sections are too low► ► Huggins cross-sections are too highHuggins cross-sections are too high

► ► All bands have problems at this level of accuracyAll bands have problems at this level of accuracy► ► Further studies are required to resolve this issue!Further studies are required to resolve this issue!

12

Summary of HITRAN 2004Summary of HITRAN 2004

HITRAN line-by-line portionHITRAN line-by-line portion ● 39 molecules, 93 isotopologues ● 39 molecules, 93 isotopologues ● 1,734,469 transitions (274 Mbytes) ● 1,734,469 transitions (274 Mbytes)

HITRAN IR Cross-sectionsHITRAN IR Cross-sections ● 30 molecules ● 30 molecules ● 860 temperature-temperature sets (153 Mbytes) ● 860 temperature-temperature sets (153 Mbytes)

http://cfa-www.harvard.edu/HITRANhttp://cfa-www.harvard.edu/HITRAN

13

14

C2F

6

(CFC

-116

)C

Cl 4

CC

l 3F(C

FC-1

1)

15

CC

lF3

(CFC

-13)

CC

l 2F2

(CFC

-12)

CF 4

(CFC

-14)

SF6

16

CH

3C(O

)OO

NO

2

(PA

N)

CC

lF2C

F 2C

HC

lF(H

CFC

-225

cb)

1 Laurence S. Rothman Harvard-Smithsonian Center for Astrophysics Atomic and Molecular Physics Division…

Documents