GSMA :

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Analysis of high resolution infrared CW-CRDS
spectra of ozone in the 6000-6750 cm-1 spectral
region
A. Barbe, M.R. De Backer-Barilly, Vl.G. Tyuterev,
D. Romanini1, S.Kassi1 , A. Campargue1
Groupe de Spectrométrie Moléculaire et
Atmosphérique, UMR CNRS 6089 Université de Reims
Champagne Ardenne France 1 Laboratoire de
Spectrométrie Physique, UMR CNRS 5588, Université
Joseph Fourier, Saint Martin dHères, France
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The compact fibered CW-CRDS spectrometer
(Grenoble)1480-1687 nm (5800-7000 cm-1)Typical
sensitivity 3?10-10 cm-1
6nm/diode 40 diodes
Lambdameter
Laser diode
nf(T,I)
Optical isolator
Coupler
AO Modulator
laser ON
Photodiode
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Illustration of the achieved sensitivity The
example of the a1?g (0)-X3Sg-(1) of O2
k810-31cm/molec
Chem. Phys. Lett. 409 (2005) 281287
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Intensity calculations
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Region ( 233-000 ) 6720 cm-1
Observed absorption coefficient (10-6 cm-1)
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on (520) in (233)
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on (520) in (242)
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Spectroscopic parameters (cm-1)
Parameter Parameter (350) (233) (171) (520) (242) (412)
EVV 6671.203 (10) 6716.536163 (80) 6728.683 (f) 6751.2465 (21) 6764.45674 (29) 6820.252 (11)
A-(BC)/2 3.230068 (85) 3.1243593 (67) 3.37 (f) 3.185396 (22) 3.200539 (14) 2.811073 (38)
(BC)/2 0.398264 (14) 0.38917245 (70) 0.3948 (f) 0.4068265 (54) 0.3929780 (11) 0.393939 (21)
(B-C)/2 0.024001 (30) 0.02663268 (95) 0.0227 (f) 0.0209819 (11) 0.02688310 (79) 0.025125 (f)
DK ?103 g 0.33969 (13) g 0.2153 (14) 0.14547 (22) g
DJK ?105 g 0.20139 (53) g g -0.8612 (23) g
DJ ?106 g 0.50785 (39) g 1.4459 (33) 0.2514 (10) g
dJ ?106 g 0.10107 (28) g g 0.13684 (28) g
dK ?105 g 0.7052 (42) g g 1.0078 (64) g
HK ?106 g 0.24415 (69) g g g g
HKJ ?107 g 0.4820 (19) g g g g
Coupling parameters
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Statistics for rovibrational transition
calculation
Vibrational transition (233)?(010) (233)?(000) (242)?(000) (520)?(000)
Band center (cm-1) 6015.605 6716.536 6764.456 6751.246
J max 37 37 46 33
Ka max 9 12 9 7
Number of transitions 322 797 797 797
r.m.s. (?103) (cm-1) 3.7 8.5 8.5 8.5
7.5
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Transition moment operator parameters (Debye)
Operator Parameters Value Number of transitions (J max, Ka max) rms deviation ()
2n1 3n2 3n3 band
d1 (104) 0.29188 (35) 213 (36, 13) 16.7
d2 (108) - 0 .3552 (23) 213 (36, 13) 16.7
d3 (107) 0.1689 (28) 213 (36, 13) 16.7
d6 (107) - 0.582 (16) 213 (36, 13) 16.7
d7 (107) - 0.554 (16) 213 (36, 13) 16.7
2n1 4n2 2n3 band
d1 (105) 0.3112 (25) 102 (42, 9) 24.0
d5 (106) - 0.46620 (49) 102 (42, 9) 24.0
2n1 3n2 3n3 n2 band
d1 (103) 0.12579 (23) 104 (33, 9) 23.4
d2 (107) - 0.7561 (28) 104 (33, 9) 23.4
d4 (106) - 0.2938 (10) 104 (33, 9) 23.4
104 (33, 9) 23.4
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Statistics for line intensities
2n1 3n2 3n3 band 2n1 3n2 3n3 band 2n1 4n2 2n3 band 2n1 4n2 2n3 band 2n1 3n2 3n3 n2 band 2n1 3n2 3n3 n2 band
Deviation Number of lines Deviation Number of lines Deviation Number of lines
158 (74.2 ) 79 (77.4 ) 74 (71.2 )
40 (18.8 ) 18 (17.6 ) 26 (25 )
15 (7 ) 5 (5 ) 4 (3.8 )

rms 16.7 rms 16.7 rms 24.0 rms 24.0 rms 21.1 rms 21.1
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Final comparison between Observed and Calculated
spectrum
Observed
Calculated
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Comparison between Obs. and Calc. spectrum in
the P branch of 2?13?23?3 (J 14)
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E (cm-1) Nb DE O-C vib J Ka Kc
6717.3035 1 -10.8 233 1 0 1
6721.1925 1 -8.8 233 3 0 3
6728.1757 2 1.4 -7.6 233 5 0 5
6738.2282 3 0.2 -7.6 233 7 0 7
6751.3204 3 0.3 -4.3 233 9 0 9
6767.4100 3 5.8 0.3 233 11 0 11
6786.4474 3 0.5 -2.6 233 13 0 13
6808.4097 4 1.5 0.2 233 15 0 15
6833.2633 3 0.2 0.6 233 17 0 17
6860.9959 2 1.1 1.4 233 19 0 19
6891.6000 4 1.4 0.8 233 21 0 21
6925.0791 4 1.0 2.5 233 23 0 23
6961.4286 4 1.8 -3.3 233 25 0 25
7000.6349 2 3.8 -3.0 233 27 0 27
7042.7524 3 0.7 -1.2 233 29 0 29
7087.7359 2 1.6 -5.5 233 31 0 31
7135.6120 1 2.7 233 33 0 33
7186.3675 1 9.7 233 35 0 35
6720.4562 1 -8.9 233 1 1 0
6721.9063 1 -8.0 233 2 1 2
6724.4815 2 0.8 -7.4 233 3 1 2
6727.1665 4 2.9 -5.4 233 4 1 4
6731.7199 5 0.8 -7.7 233 5 1 4
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Observing and assigning B type bands (?Ka 1)
in this high level range represents an
challenge. With previous work done with the
F.T.S, the highest observed bands were 2n12n3(
4141 cm-1) and 2n1n22n3 (4783 cm-1). In general
, FOR OZONE, this type of band is much more
difficult to assign than A type bands, were
strong compressed R branch appear, for several
reasons They are much weaker than A type bands
at a given energy level range. They extend over a
much larger spectral range, and , as a
consequence, are never totally observed , being
overlapped by stronger A type bands, and often
partly hidden by impurities, like H2O,CO2,CO The
general shapes of theses bands are difficult to
reproduce in a first attempt, as 6 type of
transitions may be observed, and the introduction
of unknown additional transition moment
parameters is obligatory to reproduce line
intensity observations.( as example µ 5 terms
must be introduce to reduce Q branches which
are not visible in our spectra ).
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Calculated spectra of ?12?24?3 in 3
cases (normalisation on observed lines in the
6155 cm-1 region)
All ? of A and B bands
All ? of B band ?A 0
Only ?1 for B band ( ?50)
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Observed and calculated spectrum of the n1 2n2
4n3 band in the 6156 6157 cm-1 range
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(331-000) the weakest band observed so far
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Assigned transitions in the range 60006900cm-1
Nature of the work Vibrational Assignment Band center Number of transitions J max Ka max
completed 233-010 6015.605 350 37 11

completed 034-000 6046.970 138 40 4
completed 105-000 6063.933 531 43 10
completed 510-000 6100.216 122 29 4
completed 223-000 6124.286 520 44 14
completed 124-000 6154.702 498 49 7

completed 331-000 6198.534 116 23 6

In progress 025-000 6305.039 992 39 12
In progress 501-000 6355.739 593 37 10
In progress 223-000 6386.981 548 36 11

In progress 421-000 6568.079 65 27 2
In progress 205-000 6586.969 398 37 6

completed 233-000 6716.536 483 37 12
completed 520-000 6751.246 22 33 7
completed 242-000 6764.456 399 46 9

In progress 007-000 6895.493 284 29 11

TOTAL 5959
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Vibrational state Observed Predicted (cm-1)Range 4250-5520
202 0.021
301 0.0280
023 0.288
122 -0.030
221 0.035
014 0.292
320 -0.131
113 0.279
212 0.139
311 0.433
005 0.411
104 0.584
203 -0.090
302 0.656
123 -0.094
401 0.050
015 0.136
Vibrational state Observed Predicted (cm-1)Range 5540-6780
114 0.558
015 -0.396
105 0.896
232 -1.526
105/303 0.320
510 0.808
223 -1.748
124 -0.397
331 0.712
025 -2.192
501 0.243
223/313 0.428
421 -0.227
205 -0.566
233/143 5.162
520 -1.902
242 2.757
Vl.G. Tyuterev, H. Seghir, A. Barbe, S.A.
Tashkun, Ozone molecule high energy
resonances, consistency of variational and
perturbative calculations and complete vibration
assignments up to dissociation , HRMS, Praha
2006
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Conclusion
This work , thanks to the high sensitivity of the
experimental set-up (CW-CRDS) allows to observe
many weak rovibrational transitions of ozone. All
the relatively strong or of medium intensity
are rotationally undoubtedly assigned. It
confirms previous work done with FTS, that is to
say, that above 3300 cm-1,the simplified scheme
of ozone, including poylads corresponding to the
same value of v2, with Darling-Dennison
resonances between v1,v2,v3 and v12,v2,v3 T 2
states and coriolis resonances between
v1,v2,v3and v1 T 1,v2,v3 1 states is no more
valid large vibrational couplings arise between
all states in a neighborhood, even with large
value of v2. As a result, predictions of the
strengths of interactions between various
partners become a real challenge, as the number
of possibly interacting states become obviously
larger and larger as far as energy is increasing.
Remember that highest observations are near 7000
cm-1, the dissociation limit being near 8600
cm-1. Prediction of rotational constants also is
difficult. Nevertheless, we have been able, in
two spectral regions, to complete the works, that
is to say find suitable models, for positions and
intensities which reproduce correctly ( near the
experimental accuracy) the observed spectra.
Consequently, we give for these works not only
hamiltonian parameters and transition moment
parameters, but also energy levels, corresponding
to observed transitions. It has also been
possible to reproduce B type bands, despite the
difficulties mentioned during this talk. A s
final conclusion, we will continue to advance
theoretically and experimentally, simultaneously,
to have a final good understanding of the dipole
and potential function of ozone