Revision of Spectral Parameters for the B- and γ-Bands of Oxygen and their Validation using Atmospheric Spectra with the Sun as Source 66 th International.

Revision of Spectral Parameters for the B- and γ-Bands of Oxygen

and their Validation using Atmospheric Spectra with the Sun as Source

66th International Symposium on Molecular Spectroscopy

The Ohio State University20-24 June 2011

Geoffrey C. ToonJet Propulsion Laboratory

Laurence S. Rothman, Iouli E. GordonHarvard-Smithsonian Center for Astrophysics

Importance of Molecular OxygenParameters in HITRAN

Uniformly mixed gas in terrestrial atmosphere

Bands in many spectral regions

Examples of remote-sensing applications

- Satellite missions: OCO, GOSAT, SCIAMACHY, ACE...- Disentangling chlorophyll fluorescence from

atmospheric scattering effects- Cloud-top height measurements- Wind measurements from space

Spectroscopic difficulties

- Bands are inherently weak(magnetic dipole, electric quadrupole)

- Line-shape issues- Collision Induced Absorption

a 1-g

X 3Σg-

b 1Σ+b 1Σ+g

v = 1

B-ba

nd, 0

.69

µm

v = 0

A-ba

nd, 0

.76

µm

1.27 µm

γ-ba

nd, 0

.63

µm

v = 1

v = 1

v = 0

v = 0

v = 2v = 3

Low-lying Vibronic States of Molecular Oxygenin HITRAN

447-

m W

LEF

tow

er

FTS near Tall Tower in Park Falls WI

Total Column Carbon Observing Network (TCCON)

Comparison between HITRAN and Ground-based FTS observations for Oxygen B-band

Experiment by G. Toon,at Wisconsin tower site

14400 14450 14500 14550 Wavenumber (cm-1)

RMS = 2.176%

Recorded 22 Dec 2004

Comparison between New Analysis and Ground-based FTS observations for Oxygen B-band

14400 14450 14500 14550 Wavenumber (cm-1)

RMS = 0.868%

Kitt Peak National Solar Observatory(near Tucson Arizona)

Kitt Peak Fourier Transform Spectrometer

Residuals for γ-band using: a) HITRAN2008; b) HITRAN2008 supplemented by missing 2 lines at band head; and c) new line list

Parameter(cm-1) This work Albritton et al a Cheah et al b Phillips et al c Naus et al d

T1 14526.9896(12) 14526.9909(17) 14525.65553(26

)

14526.9976(12)

B1 1.3729553(72) 1.372982(10) 1.3729659(22) 1.372951(18)

D1 5.3960(93) ×10-6 5.418(10) ×10-6 5.4086(42) ×10-6 5.397(50) ×10-6

T2 15903.7479(27) 15903.7509(16) 15902.4251(32) 15903.748(3)

B2 1.354630(23) 1.354609(11) 1.354644(38) 1.35463(2)

D2 5.484(36) ×10-6

Number of lines used in this work per band

MW: 85; Raman: 94; b1Σg+ (v=1) - a1Δg(v=0): 29; a1Δg - X 3Σg− : 199; b1Σg+ (v=1) - X 3Σg− (v=0): 72; b1Σg+ (v=2) - X 3Σg− (v=0): 49

Spectroscopic parameters of the v = 1 and 2 levels

of the b1Σg+ state of 16O2

a. Albritton DL, Harrop WJ, Schmeltekopf AL, Zare RN, J Mol Spectrosc 1973;46:103-18b. Cheah S-L, Lee Y-P, Ogilvie JF, JQSRT 2000;64:467-82c. Phillips AJ, Peters F, Hamilton PA, J Mol Spectrosc 1997;184:162-6d. Naus H, Navaian K, Ubachs W, Spectrochimica Acta Part A 1999;55:1255-62

Parameter (cm-1) This workBabcock and

Herzberg Naus et al HITRAN

T1 14490.14425(257) 14488.84 14490.145(3) 14488.826

B1 1.297296(35) 1.29740 1.29727(3) 1.29717

D1 4.897(92) ×10-6 4.80(8) ×10-6 4.6

T2 15829.5491(207) 15828.247

B2 1.28056(36) 1.279

D2 5.37(123) ×10-6 4.86 ×10-6

Number of lines used in this work per bandMW: 85; b1Σg

+ (v=1) - X 3Σg− (v=0): 72;

b1Σg+ (v=2) - X 3Σg

− (v=0): 49

Parameter (cm-1) This work Babcock and Herzberg Naus et al

T114507.5841(20)

14506.26 14507.583(2)

B11.332774(15) 1.3331 1.332761(15)

D15.031(21) ×10-6 5.11(2) ×10-6

Spectroscopic parameters of the v= 1 and 2 levels of the b1Σg+ state of 16O18O

Spectroscopic parameters of the v=1 level of the b1Σg+ state of 16O17O

Intensity Corrections Applied to B- and γ-bandsof Oxygen in HITRAN

Global correction:

All intensities in both bands were multiplied by

to remove the long standing programming error.

(-line/-band)3

B-band:

Intensities were multiplied by 1.02 to make them more consistent

with CRDS measurements by Lisak et al Phys Rev A (2010).

16O17O intensities had to be further multiplied by 1.5

γ -band:

HITRAN intensities, which were based on Mélières et al JQSRT

(1985), were found to be underestimated by 20%. Interestingly, the

intensities in Miller et al JQSRT (1976) were exactly 20% higher

and therefore became our choice.

B-band improvements for the 16O17O isotopologue

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 300.034

0.036

0.038

0.040

0.042

0.044

0.046

0.048

0.050

0.052

0.054

0.056

0.058

0.060

se

lf, cm

-1/a

tm

J'

Barnes&Hays

Lisak et al.

Empirical function from the A-band Robichaud et al.

Empirical function from the A-band Long et al.

Self-broadened half widths in the B-band

0 4 8 12 16 20 24 28 32 36-0.0125

-0.0120

-0.0115

-0.0110

-0.0105

-0.0100

-0.0095

-0.0090

-0.0085

-0.0080

-0.0075

-0.0070

-0.0065

-0.0060

-0.0055

, cm

-1

P-lines (Barnes&Hays) R-lines (Barnes&Hays)A-band P-lines*1.22A-band R-lines*1.22

J'

Pressure shifts in the B-band

Improvements of Parameters for O2

A-, B-, and γ-Bands ( level)

- Positions and intensities of transitions- Self- and air-broadened half widths- Pressure shifts- Isotopologues (16O18O, 16O17O)

b 1Σ+g

Singlet-Delta bands ( level)

- Positions and intensities of transitions- Self- and air-broadened half widths- Pressure shifts- Quadrupole transitions

a 1-g

Microwave lines ( ground state)- Positions- Intensities of high-rotational transitions- Self- and air-broadened half widths- Isotopologues (16O18O, 16O17O)

X 3Σg-

Future Improvements of Parameters for O2

Line-coupling Line shape deviations from Voigt

More laboratory controlled observations

- High sensitivity, higher rotational levels Theory: refine relative line strength formulae

Atmospheric δ-Band ( 3 ← 0 vibration at .59 μm) Add hot band (2-1)

b 1Σ+g X 3Σg

-

SAO HITRAN team membersKelly ChanceIouli GordonGang LiCyril RichardCameron Mackie

Acknowledgments

Joseph HodgesDaniel LisakLinda BrownCaroline Nowlan

Funding SupportNASA Earth Observing SystemNASA Planetary Atmospheres ProgramCooperative Research Development Foundation

NASA’s Aura mission

• EOS Aura is the last of the three main NASA EOS missions• Aura was launched from Vandenberg Air Force base in July 2004 carrying four

instrumentsHigh Resolution Dynamics Limb Sounder (HIRDLS)– An infra-red radiometer for sounding the stratosphere, mesosphere and

upper troposphere (heritage from LIMS, SAMS, ISAMS)Microwave Limb Sounder (MLS)• A microwave radiometer for sounding the stratosphere, mesosphere and

upper troposphere (heritage from UARS)Ozone Monitoring Instrument (OMI)• Measures column O3, N2O, SO2 and other species from UV/Visible solar

backscatter (heritage from TOMS)Tropospheric Emission Spectrometer (TES)• An infrared limb and nadir viewing Fourier transform spectrometer for

measuring tropospheric O3, CO and other species