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9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Formaldehyde broadening coefficients
Agnès Perrin Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), CNRS,
Université Paris XII, Créteil, France
Hamiltonian constants
David Jacquemart, Fridolin Kwabia-Tchana, and Nelly LacomeLaboratoire de Dynamique, Interactions et Réactivité (LADIR), CNRS, Université
Pierre et Marie Curie-Paris 6, France
HR FT spectra and line broadening measurements
Anne Laraia and Bob Gamache Department of Environmental, Earth & Atmospheric Sciences
University of Mass. Lowell, USA
Calculation of broadening parameters
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
- Two spectral regions of atmospheric interest:
around 3.5 µm (2600-3200 cm-1) complete update in HITRAN 2008
around 5.7 µm (1700-1800 cm-1) new line list available in HITRAN 2008
Bruker HR120-FTS spectrum recorded at LADIR
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
2 band
1, 5 + 6 other bands
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Summary of the presentation
1/ Experimental measurements of both self- and N2-broadening coefficients
2/ Empirical model for the rotational dependence of broadening coefficients
3/ Theoretical calculation of N2-broadening coefficients and their temperature exponents
4/ Comparison with literature
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Multispectrum fitting procedure
→ 284 transitions at 5.7 µm region
→ 456 transitions at 3.5 µm regionSelf-and N2-broadening coefficients
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
In HITRAN:
Self-widths fixed to 0.00 cm-1/atm
Air-widths fixed to 0.107/0.108 cm-1/atm
0 5 10 15 20 25 30
0.0
0.2
0.4
0.6
0.8
1.0
Jlow
5.7 µm spectral region 3.5 µm spectral region
Se
lf-b
roa
de
nin
g c
oe
ffic
ien
ts in
cm
-1/a
tm
0 5 10 15 20 25 30
0.06
0.08
0.10
0.12
0.14
N2-
bra
od
en
ing
co
eff
icie
nts
in c
m-1/a
tm
Jlow
5.7 µm spectral region 3.5 µm spectral region
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
0 2 4 6 80.00
0.02
0.04
0.06
0.08
0.10
0.12
Ka
N2-
bra
od
en
ing
co
eff
icie
nts
in c
m-1/a
tm
2
1
5
24
26
3+
6
Ka dependence of the N2-broadening coefficients
obtained at 3.5 and 5.7 µm
Transitions having same value of Jlow = 8
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Summary of the presentation
1/ Experimental measurements of both self- and N2-broadening coefficients
2/ Empirical model for the rotational dependence of broadening coefficients
3/ Theoretical calculation of N2-broadening coefficients and their temperature exponents
4/ Comparison with literature
0 5 10 15 20 25 30
0.06
0.08
0.10
0.12
0.14
N2-
brao
deni
ng c
oeff
icie
nts
in c
m-1/a
tm
Jlow
5.7 µm spectral region 3.5 µm spectral region
0 1 2 3 4 5 6 7 8 9 100.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
N2-
bro
ad
en
ing
co
eff
icie
nts
in c
m-1.a
tm-1
Ka"
J" = 6
0 1 2 3 4 5 6 7 8 9 100.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
J " = 8
Ka"
N2-
broa
deni
ng c
oeff
icie
nts
in c
m-1.a
tm-1
0 1 2 3 4 5 6 7 8 9 100.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
J" = 10
Ka"
N2-
broa
deni
ng c
oeff
icie
nts
in c
m-1.a
tm-1
No evidence of a vibrational dependence (5.7µm 3.6 µm)
Evidence of a J- and Ka-rotational dependence of the linewidths
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
0 10 20 30 40 500.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
Ka
2
N2-
bra
od
en
ing
co
eff
icie
nts
in c
m-1/a
tm
2
1
5
24
26
3+
6
0 2 2( )J a J J aK a a K For each set of γ having same J’’ value:
J’’ = 8
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Empirical parameters describing the J-and Ka-rotational dependence of the N2-broadening coefficients
0 2 2( )J a J JK a a K
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Empirical parameters describing the J-and Ka-rotational dependence of the self-broadening coefficients
0 2 2( )J a J J aK a a K
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Line broadening (self and by N2) can easily be calculated using these constants
JQSRT 111 (2010), 1209-1222.
0 2 2( )J a J J aK a a K
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Summary of the presentation
1/ Experimental measurements of both self- and N2-broadening coefficients
2/ Empirical model for the rotational dependence of broadening coefficients
3/ Theoretical calculation of N2-broadening coefficients and their temperature exponents
4/ Comparison with literature
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Complex Robert-Bonamy formalism
for N2-broadening coefficients
Calculation done for the 2 band
→ Constants for dipole moment of H2CO, for quadrupole of H2CO and N2 taken from literature
→ Parameters for Lennard-Jones atom-atom potential have been manually fitted to match a reduced set of N2-broadening measurements
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Comparison between
measurements, empirical model and theoretical calculation (CRB)
T = 296 K
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Comparison between
measurements, empirical model and theoretical calculation (CRB)
T = 296 K
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
CRB calculation of N2-broadening coefficients at 296 K
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Temperature exponent based on CRB formalism calculations
at various temperatures
Set of 7 temperatures:
200, 225, 275, 296, 350, 500, 700 K
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Temperature exponent from CRB calculations (200-350 K)
In HITRAN 2008:
nair fixed to 0.7
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Summary of the presentation
1/ Experimental measurements of both self- and N2-broadening coefficients
2/ Empirical model for the rotational dependence of broadening coefficients
3/ Theoretical calculation of N2-broadening coefficients and their temperature exponents
4/ Comparison with literature
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Comparison for low Ka values
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Conclusion
→ Measurements of self- and N2-line widths at 296K (for more than 700 transitions)
→ Empirical model to reproduce the rotational dependence of the measurements
→ CRB calculation of N2 widths for temperatures ranging from 200 to 700K
→ Temperature exponents for the N2-widths derived from CRB calculations
Generation of self-, air-widths, and nair for HITRAN 2008 line list
(available as supplementary materials of JQSRT 111(2010), 1209-1222.)
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
In the special issue dedicated to Larry
Thanks for your attention…
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
Sample of the 5.7-µm spectral region
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
9th HITRAN Database & Atmospheric Spectroscopy Applications conferences
0 2 2( )J a J JK a a K For each set of γ having same Jlow value:
Jlow = 8