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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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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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96 (2005) 139-204
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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
6
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