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

Atomic and Molecular Physics Division

Cambridge MA 02138, USAMolecules in the atmospheres

of extrasolar planetsParis, FRANCE

19-21 Novembre 2008

Spectroscopic ParametersSpectroscopic Parametersfor the Atmospheres offor the Atmospheres of

Extrasolar PlanetsExtrasolar Planets

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PASTPAST

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4

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Jean Baptiste Joseph FourierMarch 21, 1768 – May 16, 1830

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)

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

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HITRAN law?

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PRESENTPRESENT

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96 (2005) 139-204

10Level 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

Supplemental

Supplemental

Cross-sections

Alternate

HITRAN(line-transition

parameters)

IRCross-

sections

AerosolRefractive

Indices

LineCoupling

CO2 data

UV

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

160-character total160-character total

ParameterParameter Field sizeField size DefinitionDefinition

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

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Some New UpdatesSome New UpdatesH2O – water

►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

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G

lob

al f

it

new

1.7 μm

2.3 μm

Methane ChallengeMethane Challenge

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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]

More New Updates…..More New Updates…..

HNO3 – nitric acid

► Update 600-1790 cm-1 [Perrin et al]► Further Improvements in 11-µm region [Gomez et al]

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Species Currently Covered (line-by-line portion)Species Currently Covered (line-by-line portion)

Molecule# of isotopo-

logues Molecule# of isotopo-

logues Molecule# of isotopo-

logues

H2O 6 HCl 2 COF2 1

CO2 8 HBr 2 SF6 1

O3 5 HI 1 H2S 3

N2O 5 ClO 2 HCOOH 1

CO 6 OCS 5 HO2 1

CH4 3 H2CO 3 O 1

O2 3 HOCl 2 ClON2O 2

NO 3 N2 1 NO+ 1

SO2 2 HCN 3 HOBr 2

NO2 1 CH3Cl 2 C2H4 2

NH3 2 H2O2 1 CH3OH 1

HNO3 1 C2H2 2 CH3Br 2

OH 3 C2H6 1 CH3CN 1

HF 1 PH3 1 CF4 197 Isotopologues97 Isotopologues

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Species Currently Covered (IR Cross-sections)Species Currently Covered (IR Cross-sections)Molecule Name 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

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IUPAC Water-Vapor TaskIUPAC Water-Vapor Task

• Collect all kinds of original information about the high-resolution spectroscopy of the water molecule

Distributed Information System

• Provide active storage of these data and related metadata

• Deliver information to users in different forms via the Internet

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IUPAC vs HITRANRo-vibrational levels

for H217O

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H I T E M PH I T E M P

HITRANHITRAN

Intersection des Banques de Données Intersection des Banques de Données HITRAN et HITEMPHITRAN et HITEMP

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HITRAN vs HITEMP COHITRAN vs HITEMP CO22

• 250 ppm CO2

• 5-meter source• 100 feet above the surface

HITEMP vs HITRAN CO2 1000 K

0.00E+005.00E-051.00E-041.50E-042.00E-042.50E-043.00E-04

2100 2200 2300 2400Wavenumber

Rad

ian

ce

HITEMP

HITRAN

HITEMP vs HITRAN CO2 1500 K

0.00E+00

2.00E-04

4.00E-04

6.00E-04

8.00E-04

2100 2200 2300 2400

Wavenumber

Rad

ian

ce

HITEMP

HITRAN

HITEMP vs HITRAN CO2 1000 K

0.00E+00

2.00E-06

4.00E-06

6.00E-06

8.00E-06

3300 3400 3500 3600

Wavenumber

Rad

ian

ce

HITEMP

HITRAN

HITEMP vs HITRAN CO2 1500 K

0.00E+00

5.00E-06

1.00E-05

1.50E-05

2.00E-05

3300 3400 3500 3600

Wavenumber

Rad

ian

ce

HITEMP

HITRAN

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Comparison of CDSD and old HITEMP with MeasurementsComparison of CDSD and old HITEMP with Measurements

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HITEMPHITEMP

• 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

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New HITEMP Water List Assembly

Convert to HITRAN2004 format

Combination of BT2, high-temperature experiments, and HITRAN

HITEMPWater Line List

List created using BT2 database- for principal isotopologue, created at 296Kwith 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)

HITRANdatabase

Einstein A-coefficients,Statistical weights

Line-shape parameters(widths, shifts, etc)

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►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

Improvements and Enhancements to Improvements and Enhancements to thethe CompilationCompilation being consideredbeing considered

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AccessAccess

web site: http://cfa.harvard.edu/HITRAN

- Gives instructions for accessing compilation (free)- Updates- Documentation- Links to related databases- HITRAN facts- Related conferences

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JavaHAWKSJavaHAWKS JavaJava version of HHITRAN AAtmospheric WWorKSKStation

• Functions to manipulate and filter the HITRAN andassociated molecular spectroscopic databases

• Internet access to HITRAN and other related databases

• Links to abstracts that are the sources forHITRAN parameters

• Access to archival HITRAN documentation

• Plotting of line-by-line files and cross-section files

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Some Sources of ErrorsSome Sources of Errorsin the HITRAN Databasein 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

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HITRANHITRAN International Advisory Committee International Advisory Committee

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CC

lF3

(CF

C-1

3)C

Cl 2

F2

(CF

C-1

2)C

F4

(CF

C-1

4)

SF

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Typical Cross-section filesTypical Cross-section files

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

Comparison of different theoretical line listsComparison of different theoretical line listswith high-temperature observationwith high-temperature observation