1. Spectroscopic Parameters Molecules in the atmospheres
for the Atmospheres of
Extrasolar Planets
Laurence S. Rothman
Harvard-Smithsonian Center for Astrophysics
Atomic and Molecular Physics Division
Cambridge MA 02138, USA
Molecules in the atmospheres
of extrasolar planets
Paris, FRANCE
19-21 Novembre 2008 1

2. PAST 2

3. 3

4. 4

5. - Planets lose energy by infrared radiation
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)
Jean Baptiste Joseph Fourier
March 21, 1768 – May 16, 1830 5

6. Joseph-Marie Jacquard – 1801 Charles Babbage ~ 1820 HITRAN – 1973
Florida
Babbage once contacted the poet Alfred Tennyson in response to his poem "The Vision of Sin". Babbage wrote, "In your otherwise beautiful poem, one verse reads,
Every moment dies a man,
Every moment one is born.
... If this were true, the population of the world would be at a standstill. In truth, the rate of birth is slightly in excess of that of death. I would suggest [that the next version of your poem should read]:
Every moment 1 1/16 is born.
Strictly speaking, the actual figure is so long I cannot get it into a line, but I believe the figure 1 1/16 will be sufficiently accurate for poetry." 6

7. HITRAN law?
Like Moore’s law (number of transistors on a printed circuit doubles every 2 years). Moore’s law is a violation of Murphy’s law… HITRAN gets better and better. 7

8. PRESENT 8

9. 96 (2005) 9

10. (line-transition parameters) Global Data Files, Tables, and References
File Structure of HITRAN Compilation
JavaHAWKS Software Installers and Documentation
Level 1
Level 2
HITRAN
(line-transition parameters) IR
Cross-sections UV
Aerosol
Refractive Indices
Line
Coupling
CO2 data
Global Data Files, Tables, and References
Line-by-line
Cross-sections
Level 3
Supplemental
Supplemental
Alternate
Molecule-
by-molecule 10

11. HITRAN Line-by-line Parameters
Field size
Definition
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 296K]
Aif
E10.3
Einstein A-coefficient [s-1]
γair
F5.4
Air-broadened half-width (HWHM) 296K]
γself
F5.4
Self-broadened half-width (HWHM) 296K] E″
F10.4
Lower-state energy [cm-1]
nair
F4.2
Temperature-dependence coefficient of γair
δair
F8.6
Air pressure-induced shift 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
160-character total 11

12. 12

13. Some New Updates H2O – water CO2 – carbon dioxide CH4 – methane
►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 cm-1 [Brown et al]
► Line-shape calculations, supplemented with exp.
CH4 – methane 13

14. Methane Challenge
 Global fit 
1.7 μm
2.3 μm
new 14

15. More New Updates….. O3 – ozone O3 – ozone O3 – ozone O3 – ozone
► Major update 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]
HNO3 – nitric acid
► Update cm-1 [Perrin et al]
► Further Improvements in 11-µm region [Gomez et al] 15
O3 – ozone
O3 – ozone
O3 – ozone
A major update has been made for the first three isotopologues of ozone, thanks to the Reims-Tomsk collaborative effort [ The new data cover bands in the spectral range 1632 to 5870 cm-1, thereby extending the short wavelength coverage of HITRAN. In addition, an improved algorithm for incorporating ozone line-shape parameters has been applied to all ozone bands in the compilation.
O3 – ozone
A major update has been made for the first three isotopologues of ozone, thanks to the Reims-Tomsk collaborative effort [ The new data cover bands in the spectral range 1632 to 5870 cm-1, thereby extending the short wavelength coverage of HITRAN. In addition, an improved algorithm for incorporating ozone line-shape parameters has been applied to all ozone bands in the compilation.
A major update has been made for the first three isotopologues of ozone, thanks to the Reims-Tomsk collaborative effort [ The new data cover bands in the spectral range 1632 to 5870 cm-1, thereby extending the short wavelength coverage of HITRAN. In addition, an improved algorithm for incorporating ozone line-shape parameters has been applied to all ozone bands in the compilation.
A major update has been made for the first three isotopologues of ozone, thanks to the Reims-Tomsk collaborative effort [ The new data cover bands in the spectral range 1632 to 5870 cm-1, thereby extending the short wavelength coverage of HITRAN. In addition, an improved algorithm for incorporating ozone line-shape parameters has been applied to all ozone bands in the compilation.

16. Species Currently Covered (line-by-line portion)
Molecule
# of isotopo-logues
H2O 6
HCl 2
COF2 1
CO2 8
HBr
SF6 O3 5 HI
H2S 3
N2O
ClO
HCOOH CO
OCS
HO2
CH4
H2CO O O2
HOCl
ClON2O NO N2
NO+
SO2
HCN
HOBr
NO2
CH3Cl
C2H4
NH3
H2O2
CH3OH
HNO3
C2H2
CH3Br OH
C2H6
CH3CN HF
PH3
CF4
97 Isotopologues 16

17. Species Currently Covered (IR Cross-sections)
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 17

18. 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 18

19. Ro-vibrational levels
IUPAC vs HITRAN
Ro-vibrational levels
for H217O 19

20. Intersection des Banques de Données HITRAN et HITEMP20

21. HITRAN vs HITEMP CO2 250 ppm CO2 5-meter source
100 feet above the surface 21

22. Figure 4. Comparison of CDSD and old HITEMP with measurments at 1550K
Comparison of CDSD and old HITEMP with Measurements 22

23. HITEMP Line-absorption parameters in HITRAN format Constituents
- Water Vapor: 0 to K,1500K
- Carbon Dioxide: 400 to K
- Carbon Monoxide: 0 to solar temperature
- Hydroxyl Radical: 0 to 23

24. New HITEMP Water List Assembly
List created using BT2 database
- for principal isotopologue, created at 296K
with 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)
HITRAN
database
Convert to HITRAN2004 format
Combination of BT2, high-temperature experiments, and HITRAN
Einstein A-coefficients,
Statistical weights
Line-shape parameters
(widths, shifts, etc)
HITEMP
Water Line List 24

25. 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 25

26. Access web site: http://cfa.harvard.edu/HITRAN
Gives instructions for accessing compilation (free)
Updates
- Documentation
- Links to related databases
- HITRAN facts
- Related conferences 26

27. JavaHAWKS Java version of HITRAN Atmospheric WorKStation
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 27

28. Some Sources of Errors in 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 28

29. HITRAN International Advisory Committee29

30. Typical Cross-section files
(CFC-12)
CCl2F2
(CFC-13)
CClF3
(CFC-14)
CF4
SF6 30

31. Figure 1. Comparison of different theoretical line lists with high-temperature experiments
with high-temperature observation 31