High Sensitivity CRDS of the
1
3
a Dg — X Sg Band of Oxygen near 1.27
micron: Magnetic Dipole and Electric
Quadrupole Transitions in Spectra of
Five Isotopologues
Olga Leshchishina, Samir Kassi,
Le Wang, Iouli E. Gordon,
Laurence S. Rothman, Alain Campargue
Lowest electronic states of O2
0.76 µm
M1- Magnetic dipole
E2- Electric quadrupole
b 1Σ+g
E2
M1>> E2
•
1.27 µm
M1, E2
M1, E2
a 1Dg
X
3Σ g
•
Remote sensing in relation to
high-accuracy measurements
of atmospheric greenhouse
gases such as CO2 and CH4
– Uniform mixing of oxygen
provides calibration and
removes systematic errors
– ASCENDS mission
Nightglow in planetary
atmospheres
Parameters used in HITRAN
2000-2008
• Line positions are based on the high-quality MW constants of the
excited state and unpublished term value of Brault for principal
isotopologue.
• For the 16O18O species outdated rotational constants from Herzberg
and Herzberg (Astrophys J 1947;105:353) are used for the upper
state with term value fixed to unpublished FTS spectrum.
• No 16O17O parameters in excited state are published and the lines
are not tabulated in HITRAN (their intensities are fairly weak).
• Rotational constants of 18O2 are available through microwave
measurements, but no parameters are available in the excited state
for 17O18O and 17O2 .
Electric quadrupole lines found in
solar absorption spectrum
See tomorrow talk WF03
N=9
F2
F1
F3
9
10
8
Q(9)Q(9)
P(9)P(9)
DJ=±1
P(9)Q(8)
R(9)Q(10)
O(9)P(8)
Q(9)R(8)
R(9)R(9)
O(9)O(9)
DJ=±2
Q(9)P(10)
S(9)R(10)
N(9)O(8)
P(9)O(10)
Notation of
branches:
ΔN(N'')ΔJ(J'')
S(9)S(9)
J
R(9)S(8)
T(9)S(10)
Selection rules (16O2)
DJ=0
12
e
11
f
10
e
9
f
8
e
7
f
6
e
f
e
e
CRDS measurements in Grenoble
6nm/diode
30 DFB diodes
Laser diode
Lambdameter
n=f(T,I)
Optical isolator
laser ON
-50
threshold
Laser OFF
0
Coupler
AO
Modulator
100
50
K
J
K
J
Photodiode
Routine sensitivity:
10-10 cm-1, ie 1 % absorbance
for 300 km path length
Large dynamic range of the measured
intensities: absorption coefficients from
10-5 to 10-10 cm-1 are measured on a
single spectrum
Complete set of CRDS measurements
Intensity (cm/molecule)
1E-25
66(0-0)
66(1-1)
66(0-0) Quadrupole
1E-26
1E-27
1E-28
1E-29
1E-30
7700
7800
7900
-1
Wavenumber (cm )
Fig.4
Measurements in 16O, 18O and 17O enriched mixtures!!!
Leshchishina et al JQSRT (in press)
Extract from the spectrum
Unresolved hyperfine structure
Resolving Hyperfine Structure
16
17
O O
Room temperature
0.04
-6
-1
Absorption coefficient (10 cm )
R1R1
17
0.02
O2
0.00
T=77 K
0.3
0.2
0.1
0.0
7888.6
7888.8
7889.0
-1
Wavenumber (cm )
7889.2
Measured transitions
Isotopologue
HITRAN
notation
Abundance
Band
16
16
O2
66
0.995
16 18
68
67
3.8×10-3
7.9×10-4
18
O2
88
0.94
16 18
68
78
66
4.9×10-2
~1×10-2
~1×10-3
O O
16 17
O O
O O
17 18
O O
16
O2
Number
of lines
Intensity range
(×10-26 cm/molecule)
97
23
79
127
51
3.9×10-4 – 11.0
1.0×10-4 – 1.9×10-2
1.1×10-4 – 6.4×10-3
4.3×10-4 – 1.9×10-2
3.1×10-4 – 5.8×10-3
139
22
94
203
140
53
2.0×10-4 – 10.1
1.1×10-4 – 6.0×10-3
1.1×10-4 – 8.1×10-3
1.6×10-4 – 3.4×10-1
3.3×10-4 – 6.4×10-2
1.1×10-4 –1.3×10-2
O sample
(0-0)
(0-0) elec. quad.
(1-1)
(0-0)
(0-0)
18
O sample
(0-0)
(0-0) elec. quad.
(1-1)
(0-0)
(0-0)
(0-0)
CRDS vs HITRAN (2009 update)
0.003
0.002
16
16
0.002
-1
-1
Obs. - HITRAN (cm )
0.001
Obs. - HITRAN (cm )
18
O O3
O2
0.000
-0.001
-0.002
-0.003
1E-29
0.001
0.000
-0.001
-0.002
1E-28
1E-27
1E-26
Intensity (cm/molecule)
1E-25
-0.003
1E-28
1E-27
Intensity (cm/molecule)
Comparison with Cheah et al
Cheah et al. (JQSRT 2000;64:467-82)
Water test
Refit of MW hyperfine structure
Cazzoli et al., Nuovo Cimeto B Serie 1981; 62:243-54
H eff  BN2  DN4  HN6  [  D N2  H N4 ] 23 (3 Sz2  S2 )  [   D N2   H N4 ]N  S
H hfs  bF I  S  c( I z S z  I  S ) 
1
3
16
Parameters
O17O (SPFIT)
16
O17O [Cazzoli et al]
e 2 Qq ( 3I z2  I ( I 1))
4 I ( 2 I 1 )
17
O18O (SPFIT)
17
O18O [Cazzoli et al]
−
X 3Σg
B
D
λ
λD
γ
γD
bF or b
c
eQq
Number of
lines
1.39533197(324)
4.5071×10-6
1.98471102(30)
1.88847(375)×10-6
-8.176597(86)×10-3
-7.005(614)×10-9
-1.826076(307)×10-3
4.67255(79)×10-3
-2.713(80)×10-4
1.39531862(333)
4.623×10-6
1.984709368(333)
1.91799(667)×10-6
-8.176123(133)×10-3
-8.0(10)×10-9
-3.383707(166)×10-3
4.66089(100)×10-3
-2.769(100)
1.31549483(247)
4.023×10-6
1.98463280(148)
1.7827(96)×10-6
-7.70715(13)×10-3
-7.44(123)×10-9
-1.82614(70)×10-3
4.67277(287)×10-3
-2.733(158)×10-4
1.31549006(333)
4.102×10-6
1.98463298(133)
1.8012(167)×10-6
-7.706965(233)×10-3
-9.01(200)×10-9
-3.384341(333)×10-3
4.6592(20)×10-3
-2.602(167)
59
59
30
30
rms
0.039 MHz
0.06 MHz
0.042 MHz
0.07 MHz
Additional data used in the fit
• MW data from Drouin et al (JQSRT 2010;111:1167-1173) and
references therein for 16O2, 18O2, 16O18O. For
al data was used.
16O18O
also Cohen et
• Raman data Rouillé et al. (J Mol Spectrosc 1992;154:372-82) for
16O
2
and Edwards et al. (J Raman Spectrosc 1981;10:60-3) for 18O2.
• For 16O17O and 17O18O parameters in the ground state were fixed to
those of refit of Cazzoli et al.
F ( J )  T  B J ( J  1)  D [ J ( J  1)]  H [ J ( J  1)]
2
3
Results of the fit
16
18
O2
Parameters
a)
E
B
D
H
λ
λD
λH
γ
γD
γH
X
v=0
1.437675974(19)
4.840356(76)×10-6
v=1
1556.389914(147)
1.42186406(64)
4.83954(42)×10-6
1.984751193(50)
1.946930(325)×10-6
9.71(30)×10-12
-8.42537356(584)×10-3
-8.1183(223)×10-9
4.84(153)×10-14
1.98957881(13)
2.11277(98)×10-6
O2
3 −
Σg
-8.445758(19)×10-3
-8.349(79)×10-9
v=0
1.278008448(57)
3.82252(39)×10-6
-5.20(494)×10-13
1.9845955423(417)
1.721382(233)×10-6
7.719(242)×10-12
-7.48670002(457)×10-3
-6.4111(160)×10-9
-3.80(113)×10-14
v=1
1468.4442(33)
1.2647600(12)
3.82558(727)×10-6
1.989117019(166)
1.85292(127)×10-6
1.614(213)×10-11
-7.5038322(130)×10-3
-6.4108(267)×10-9
a1Dg
T
B
D
H
v=0
7883.756645(113)
1.417839039(38)
5.102256(243)×10-6
-2.395(283)×10-12
v=1
9367.208821(267)
1.40072433(17)
5.1211(41)×10-6
-4.97(313)×10-12
Number of
lines
MW: 85
Raman: 94
This work: 199
rms
3.48×10-2MHz
Total: 378
2.48×10-3 cm-1
1.13×10-3 cm-1
v=0
7886.409277(117)
1.260409499(56)
4.029678(664)×10-6
-1.855(617)×10-12
MW: 78
v=1
9286.2239(33)
1.2460722(28)
4.04700(827)×10-6
Raman: 26
This work: 255
Total: 359
2.48×10-2 MHz 68.1×10-3 cm-1 0.77 ×10-3 cm-1
Results of the fit
16
O18O
Parameters
B
D
λ
λD
λH
γ
γD
16
O17O
17
O18O
−
X 3Σg
1.3578522686(414)
4.31692(53)×10-6
1.984674291(162)
1.833535(842)×10-6
9.50(81)×10-12
-7.956001(11)×10-3
-7.318(15)×10-9
1.39533197
4.5071×10-6
1.98471102
1.88847×10-6
1.31549483
4.023×10-6
1.98463280
1.7827×10-6
-8.176597×10-3
-7.005×10-9
-7.70715×10-3
-7.44×10-9
a 1Dg
T
B
D
Number of
lines
rms
7885.06789(13) b)
1.33913493(10)
4.552623(674)×10-6
7884.4476(11)
1.3761054(91)
4.795(16)×10-6
7885.77532(63)
1.2973728(86)
4.2413(43)×10-6
MW: 85
This work: 208
This work: 51
This work: 140
6.73×10-2 MHz
0.69×10-3 cm-1
2.35×10-3 cm-1
2.57×10-3 cm-1
Conclusions
• HITRAN data is Ok, but will be updated and extended to
add quadrupole transitions (1-1) band of 16O2 and (0-0)
band of 16O17O.
• Quality of constants for the exited state is improved. In
part through extended rotational analyses.
• For less abundant isotopologues measurements in the
upper state reported for the first time.
Acknowledgements
• S. Yu (JPL)
• NASA and ANR
THANK YOU FOR ATTENTION