Journal of Molecular Spectroscopy 210, 2840 (2001)

doi:10.1006/jmsp.2001.8434, available online at http://www.idealibrary.com on

Emission Spectrum of Hot HDO in the 3802190 cm1 Region

T. Parekunnel, P. F. Bernath, ,1 N. F. Zobov,,2 S. V. Shirin,,2 Oleg L. Polyansky,,2 and Jonathan Tennyson
Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1; and Department of Physics and Astronomy,
University College London, London WC1E 6BT, United Kingdom
E-mail: bernath@uwaterloo.ca, j.tennyson@ucl.ac.uk
Received May 29, 2001; published online September 27, 2001

Fourier transform emission spectra were recorded using a mixture of H2 O and D2 O at a temperature of 1500 C. The spectra
were recorded in three overlapping sections and cover the wavenumber range 3802190 cm1 . A total of 22 106 lines were
measured, of which 60% are thought to belong to HDO. A total of 6430 HDO transitions are assigned, including the first
transitions to the (040) vibrational state, with a term value of 5420.042 cm1 . A total of 1536 new energy levels of HDO
belonging to the (000), (010), (020), (030), and (040) states are presented, significantly extending the degree of rotational
C 2001 Elsevier Science
excitation compared to previous studies.
Key Words: water vapor; infrared spectrum; emission; line assignments; hot bands.

In molecular physics, the HDO energy levels can be used to

study the breakdown of the BornOppenheimer approximation.
At the moment, this breakdown is the largest source of error in
the calculation of water vibrationrotation energy levels from
an ab initio potential energy surface. The potential surface can
be corrected empirically (910), but recently Schwenke (14)
calculated ab initio a complete set of corrections for the breakdown of the BornOppenheimer approximation in water. The
experimental energy levels of both HDO and H2 O are needed
for comparison with theory. The HDO molecule is also a popular molecule for mode-selective laser chemistry by dissociation
(e.g., 15).
The infrared spectra of HDO were first measured by Benedict
et al. (16) in 1956, followed by work in France (e.g., 17). Since
then there has been considerable additional work, mainly by Toth
and co-workers (1823) on the room temperature infrared absorption spectra. Toth has recently published a list of the energy
levels for the (000), (010), (100), and (020) vibrational states
of HDO. Note that we adopt the traditional labeling convention
of v1 for the OD stretching mode and for the v3 OH stretching
mode, in spite of the Mulliken convention (24). Other infrared
measurements include the detection of several transitions
near 1 m by Bykov et al. (25, 26) and the 300000 and 111
000 bands by Hu et al. (27).
The pure rotational lines of HDO were measured in the submillimeter wave region by Messer et al. (28) and by Baskakov
et al. (29). To higher frequency, the pure rotational transitions
in the regions 20350 cm1 (30) and 110500 cm1 (31) were
recorded by Fourier transform absorption spectroscopy.
The most highly excited levels of HDO have been recorded
by overtone spectroscopy in the visible and near-UV regions.

1. INTRODUCTION

In recent years there has been great progress in the experimental and theoretical understanding of the energy level structure of
water (1). On the experimental side, new overtone spectra of
water have been recorded in the visible and near UV regions
(23). In the infrared, new spectra of hot water emission have
now been measured (47) from 400 to 6000 cm1 in the laboratory. Hot water vapor lines have also been seen in absorption
in the spectra of sunspots (4, 6, 8) (Water on the Sun). On the
theoretical side, the availability of high quality ab initio potential energy surfaces (9) and the direct variational calculation of
vibrationrotation energy levels have revolutionized the analysis
of water spectra (10).
Progress for the HDO isotopomer has been much less satisfactory. In particular, no spectra of hot HDO have been analyzed
to date. We report such observations in this paper.
The HDO molecule is of interest for a number of reasons.
Because H2 O is so abundant in our atmosphere, HDO can be
detected readily in atmospheric absorption spectra using the sun
as a source (11). Astrophysicists are also interested in HDO
because nearly all of the deuterium now in the Universe was
formed in the Big Bang (12). The D/H ratio is thus an important
parameter with cosmological significance. The ratio D/H can be
determined for objects such as comets from the relative HDO to
H2 O abundances (13).
1 Also Department of Chemistry, University of Arizona, Tucson, Arizona
85721.
2 Permanent address: Institute of Applied Physics, Russian Academy of Science, Uljanov Street 46, Nizhnii Novgorod, Russia 603950.

0022-2852/01 $35.00

C 2001 Elsevier Science

All rights reserved

28

29

EMISSION SPECTRUM OF HOT HDO

Most notably, Campargue and co-workers (3236) have recently used the ultrasensitive technique of intracavity laser
absorption spectroscopy to measure a number of overtone bands.
Our contribution in this area has been to record long-path Fourier
transform absorption spectra in the region 16 30022 800 cm1
(37). The most highly excited vibrational state known to date
is (007) with a band origin at 22 625.50 cm1 (37). Other experiments on HDO are the intracavity Fourier transform measurements of the 500000 transition (38), as well as Russian
intracavity measurements of the (003) and (005) levels (39).

2. EXPERIMENTAL DETAILS

The hot HDO emission spectra were recorded on November

6, 1997 at the University of Waterloo with a Bruker IFS 120HR
Fourier transform spectrometer. The spectrometer was operated
with a KBr beamsplitter and either a Si : B or a HgCdTe detector.
The spectra reported here in the region 3502200 cm1 were
recorded in three pieces. The section 350750 cm1 used a
liquid-He-cooled Si : B detector and a cold longwave pass filter
at 750 cm1 . A separate cold bandpass filter was used to cover
the region 7501300 cm1 . The region 12002200 cm1 was
recorded with a HgCdTe detector and an uncooled 2200 cm1
longwave pass filter. Forty-five scans were co-added with
the Si : B detector and forty with the HgCdTe detector at a
resolution of 0.01 cm1 .
A KRS-5 window was used on the emission port of the spectrometer. The water vapor was heated in the center of a 1-mlong, 5-cm-diameter alumina tube sealed with cooled KRS-5
windows. The tube was placed inside a furnace and heated to
1500 C. A slow flow of water vapor through the cell was maintained at a pressure of 2.5 Torr. An equimolar mixture of H2 O
and D2 O liquids was used to provide the vapor. The thermal
emission from the cell was focused into the emission port of the
spectrometer with an off-axis parabolic mirror. The lines were
measured with the PC-Decomp program of Brault and has an
estimated accuracy of 0.001 cm1 for strong unblended lines.
The spectrum, however, was very dense with H2 O, D2 O and
HDO lines present.
The three spectra analyzed for this paper have lines in the
regions 380746, 7501249, and 12502180 cm1 . There were
enough strong common lines in the two higher wavenumber
spectra to put them on a common wavenumber scale and then
calibrate them with the water lines reported in Polyansky et al.
(40). Because of a lack of strong common lines between the two
lower wavenumber regions, the lines in the region 380746 cm1
were just calibrated with our previous measurements (40) in this
region. This means that in the region 7502190 cm1 our lines
have a wavenumber scale that is in excellent agreement with
that of Toth (41, 42), but the region 380746 cm1 is on a scale
slightly different from that of Toth. Fortunately, this difference
is less than 0.001 cm1 , our estimated absolute accuracy.

3. LINE ASSIGNMENTS

A total of 22 106 lines were measured in the emission spectrum. Of course not all of these transitions correspond to HDO
and before starting detailed analysis of these lines it was necessary to eliminate those due to H2 O and D2 O. The H2 O lines
were identified by comparison with previously published (5, 6)
hot emission spectra. For D2 O similar comparisons were made
with a pure D2 O emission spectrum recorded in Waterloo
which is yet to be fully analyzed; in practice this D2 O spectrum contained approximately 10% HDO. As the intensities differ in the three regions of the HDO spectrum, these regions
were analysed separately. Lines were identified as H2 O or D2 O
by matching both frequency and intensity. This is because the
line density of the spectra is such that inevitably some HDO
lines coincide with lines from the other isotopomers. We identified 4155 H2 O lines (322 also belonging to HDO) and 5423
D2 O (447 also HDO). H2 O and D2 O lines are marked in the
full linelist which is given in the supplementary data for this
article.
Energy levels for the ground, (010), (020), (030), (100), (001),
and (110) vibrational states of HDO with low J and K a values
have been given by Toth (18, 19, 21, 22). These were used to
conduct an initial analysis of the spectrum to identify trivial
assignments were both upper and lower energy levels were already known.
To identify transitions involving previously unobserved energy levels in the system it was necessary to use variational
predictions to aid the assignment process. There is no linelist
available to us for hot HDO, but Partridge and Schwenke (9)
have computed a room temperature linelist with states extending to energies about 8000 cm1 above the ground state.
This linelist was transformed to a temperature of 1800 K using
Boltzmann statistics. The spectral region 3802190 cm1
covers both pure rotational transitions of HDO, particularly
with high J or K a , and the first bending fundamental, with
a band origin at 1403.48 cm1 , as well as associated hot
bands.
Trivial assignments and other isotopomers having been eliminated from our list of transitions, the unassigned lines were
analyzed using a computer program. Candidate transitions were
identified using the variational linelist and then confirmed, or
otherwise, by the presence, or not, of the appropriate combination difference transitions. In this way we were able to identify
numerous new transitions involving known vibrational states
and also to identify 190 transitions involving the (040) bending
state.
The Partridge and Schwenke linelist (9) proved to be too restricted for the analysis of hot rotational levels. However, they
also provided (43) energy levels for higher states of HDO.
These were used to provide estimates of frequencies for pure
rotational transitions which were then used to seed a further
search.

C 2001 Elsevier Science

30

PAREKUNNEL ET AL.

TABLE 1
Summary of Assigned HDO
Emission Lines
Transition

TABLE 2
Experimental Term Values in cm1 for the Ground and
(010) Vibrational States of HDO

Number
Pure rotations

000-000
010-010
020-020
030-030

516
372
170
77
Bending modes

010-000
020-010
030-020
040-030
110-010
011-001

1723
1676
1011
74
362
123
Difference bands

100-010
110-020

65
132

We have assigned 1146 pure HDO rotational transitions

spanning all HDO states up to (110). A total of 5085 transitions were assigned to bending transitions which involve a
change of one quantum in the 2 mode. In addition 199 transitions were assigned to assorted difference bands. It has already been found that these difference bands are common in
the emission spectrum of hot H2 O (5, 44). Table 1 gives a
summary of all bands for which more than 10 transitions were
assigned.
Experimental energy levels, which can be calculated by
linking known energy levels and newly assigned transitions,
are an important product of our analysis. This work has
more than tripled the number of known energy levels for the
states (000), (010), (020), (030) and (040). Tables 2 and 3
present energy levels for the first four of these states. The
lowest J levels have been omitted from these tabulations as
they have been well-determined previously (18, 19). Our results for the previously unobserved (040) state are given in
Table 4.
Altogether we have assigned 6430 HDO transitions in the
emission spectrum. This number represents approximately half
the transitions which we identify as belonging to HDO. There
is no doubt that many of the unassigned lines in the lower
wavenumber portion of the spectrum belong to pure rotational
transitions of vibrational states with excited stretching modes.
Analysis of these states is best conducted in conjunction with
analysis of associated vibrational transitions involving these
stretching modes. Such transitions lie to somewhat higher frequency than the spectra reported here. An emission spectrum
covering this region has been recorded in Waterloo and will
be analyzed together with the unassigned transitions remaining
from the present study.

Ka

Kc

(000)

11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
13
13
13
13
13
13
13

0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11
12
12
0
1
1
2
2
3
3

11
11
10
10
9
9
8
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
12
12
11
11
10
10
9
9
8
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
13
13
12
12
11
11
10

916.029
916.124
1046.474
1049.124
1141.691
1164.510
1206.754
1278.438
1287.239
1410.566
1411.319
1570.061
1570.095
1757.340
1757.341
1971.030
1971.030
2209.906
2209.906
2472.974
2472.974
2759.426
2759.426
1075.715
1075.762
1220.028
1221.536
1331.217
1347.119
1405.125
1465.831
1481.443
1598.066
1599.798
1756.284
1756.384
1942.372
1942.375
2155.016
2155.016
2392.886
2392.886
2654.916
2654.916
2940.256
2940.256
3248.227
3248.227
1247.964
1247.988
1405.818
1406.656
1532.728
1543.243
1618.698

a
d

C 2001 Elsevier Science

From Toth (18).

Levels treated as degenerate.

(010))
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
d
d
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
d
d
d
d
d
d
a
a
a
a
a
a
a

2316.312
2316.446
2459.361
2462.887
2561.580
2589.750
2632.660
2716.170
2724.463
2863.369
2864.036
3040.100
3040.129
3246.058
3246.059
3479.363
3479.363
3738.413
3738.413
4021.937
4021.937
4328.919
4328.919
2474.835
2474.904
2633.352
2635.417
2752.926
2773.107
2832.490
2904.291
2919.136
3051.433
3052.969
3226.829
3226.912
3431.571
3431.573
3663.801
3663.801
3921.804
3921.804
4204.229
4204.229
4510.028
4510.028
4838.388
4838.388
2645.775
2645.811
2819.396
2820.577
2956.268
2970.013
3047.832

a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
d
d
d
d
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
d
d
d
d
d
d
a
a
a
a
a
a
a

31

EMISSION SPECTRUM OF HOT HDO

TABLE 2Continued
J

Ka

Kc

(000)

13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
15
15
15
15
15
15
15
15
15
15
15

4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11
12
12
13
13
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11
12
12
13
13
14
14
0
1
1
2
2
3
3
4
4
5
5

10
9
9
8
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
14
14
13
13
12
12
11
11
10
10
9
9
8
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
15
15
14
14
13
13
12
12
11
11
10

1668.095
1693.446
1801.207
1804.840
1958.125
1958.383
2142.829
2142.841
2354.274
2354.274
2591.018
2591.018
2851.907
2851.907
3136.039
3136.039
3442.703
3442.703
3771.349
3771.349
1432.747
1432.758
1603.905
1604.362
1745.896
1752.537
1846.401
1884.843
1922.888
2019.821
2026.831
2175.564
2176.177
2358.688
2358.721
2568.783
2568.783
2804.271
2804.271
3063.912
3063.912
3346.714
3346.714
3652.000
3652.000
3979.121
3979.121
4327.677
4327.677
1630.024
1630.029
1814.319
1814.565
1970.655
1974.708
2087.137
2115.644
2169.061
2253.675
2266.175

TABLE 2Continued
(010))

a
a
a
a
a
a
a
a
a
a
a
a
a
a
d
d
d
d
d
d
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
d
d
d
d
d
d
d
d
a
a
a
a
a
a
a
a
a
a
a

3107.381
3131.745
3255.187
3258.418
3429.192
3429.410
3632.524
3632.533
3863.529
3863.529
4120.363
4120.363
4401.589
4401.589
4706.101
4706.101
5033.060
5033.060
5381.836
5381.836
2829.106
2829.125
3017.575
3018.240
3171.148
3180.106
3277.601
3325.047
3362.052
3474.478
3480.745
3647.170
3647.687
3848.900
3848.926
4078.518
4078.518
4334.055
4334.055
4613.975
4613.975
4917.099
4917.099
5242.558
5242.558
5589.694
5589.694
5958.044
5958.044
3024.796
3024.805
3227.938
3228.307
3397.438
3403.071
3520.662
3556.859
3609.422
3709.077
3720.348

a
a
a
a
a
a
a
a
a
a
d
d
d
d
d
d
d
d
d
d
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
d
d
d
d
d
d
d
d
d
d
d
d
d
d
a
a
a
a
a
a
a
a
a
a
a

Ka

Kc

(000)

15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
17
17
17
17
17
17
17

6
6
7
7
8
8
9
9
10
10
11
11
12
12
13
13
14
14
15
15
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11
12
12
13
13
14
14
15
15
16
16
0
1
1
2
2
3
3

10
9
9
8
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
16
16
15
15
14
14
13
13
12
12
11
11
10
10
9
9
8
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
17
17
16
16
15
15
14

2408.557
2409.903
2589.973
2590.057
2798.509
2798.513
3032.606
3032.606
3290.888
3290.888
3572.309
3572.309
3876.050
3876.050
4201.580
4201.580
4548.373
4548.373
4916.149
4916.149
1839.754
1839.757
2037.056
2037.188
2207.117
2209.513
2339.944
2360.075
2430.992
2502.437
2523.127
2657.013
2659.764
2836.617
2836.823
3043.420
3043.431
3275.978
3275.978
3532.781
3532.781
3812.705
3812.705
4114.878
4114.878
4438.651
4438.651
4783.618
4783.618
5149.378
5149.378
5535.745
5535.745
2061.897
2061.898
2272.103
2272.172
2455.379
2456.767
2604.144

C 2001 Elsevier Science

(010))
a
a
a
a
a
a
a
a
d
d
d
d
d
d
d
d
d
d
d
d
a
a
a
a
a

a
a
a

a
a
a
a
a
d
d
d
d
d
d
d
d
d
d
d
d
d
d
a
a
a
a
a

3880.715
3881.850
4080.660
4080.742
4308.719
4308.722
4562.833
4562.833
4841.335
4841.335
5142.978
5142.978
5466.838
5466.838
5812.270
5812.270
6178.683
6178.683
6565.872
6565.872
3232.804
3232.809
3450.501
3450.705
3635.201
3638.648
3776.003
3802.374
3872.934
3958.678
3977.541
4129.736
4132.058
4327.808
4327.975
4554.094
4554.090
4806.638
4806.638
5083.618
5083.618
5383.681
5383.681
5705.846
5705.846
6049.390
6049.390
6413.860
6413.860
6798.868
6798.868
7204.241
7204.241
3453.092
3453.094
3685.259
3685.371
3884.565
3886.630
4042.765

a
a

d
d
d
d
d
d
d
d
d
d
d
d
d
d
a
a
a
a
a
a

d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
a
a
a
a
a
a

32

PAREKUNNEL ET AL.

TABLE 2Continued
J

Ka

Kc

(000)

17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18

4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11
12
12
13
13
14
14
15
15
16
16
17
17
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11
12
12
13
13
14
14
15
15
16

14
13
13
12
12
11
11
10
10
9
9
8
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
18
18
17
17
16
16
15
15
14
14
13
13
12
12
11
11
10
10
9
9
8
8
7
7
6
6
5
5
4
4
3
3

2617.726
2707.595
2765.744
2797.620
2920.783
2926.032
3098.595
3099.058
3303.477
3303.503
3534.342
3534.342
3789.538
3789.538
4067.863
4067.863
4368.360
4368.360
4690.352
4690.352
5033.327
5033.327
5397.011
5397.011
5781.098
5781.098
6185.485
6185.485
2296.384
2296.384
2519.416
2519.452
2715.533
2716.330
2879.423
2888.238
2997.706
3043.157
3089.176
3199.653
3209.060
3375.825
3376.824
3578.631
3578.700
3807.626
3807.623
4061.120
4061.120
4337.716
4337.732
4636.448
4636.448
4956.561
4956.561
5297.521
5297.521
5658.963
5658.963
6040.706

d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
a
a
a
a

d
d

d
d
d
d
d
d
d
d
d

TABLE 2Continued
(010))

Ka

Kc

(000)

4061.184
4151.511
4222.914
4252.371
4394.100
4398.558
4590.252
4590.627
4814.593
4814.593
5065.396
5065.396
5340.750
5340.750
5639.141
5639.141
5959.524
5959.524
6301.143
6301.143
6663.518
6663.518
7046.250
7046.250
7449.132
7449.132
7872.136
7872.136
3685.619
3685.619
3932.188
3932.250
4145.632
4146.842
4320.513
4332.875
4443.997
4501.367
4544.524
4673.591
4681.624
4867.944
4868.733
5090.161
5090.218
5339.075
5339.124
5612.657
5612.668
5909.282
5909.282
6227.795
6227.795
6567.408
6567.408
6927.609
6927.609
7307.960
7307.960
7708.295

18
18
18
18
18
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20

16
17
17
18
18
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11
12
12
13
13
14
14
15
15
16
16
17
17
18
18
19
19
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8

2
2
1
1
0
19
19
18
18
17
17
16
16
15
15
14
14
13
13
12
12
11
11
10
10
9
9
8
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
20
20
19
19
18
18
17
17
16
16
15
15
14
14
13
13

6040.706
6442.540
6442.540
6864.423
6864.423
2543.209
2543.209
2778.949
2778.969
2987.607
2988.058
3165.744
3171.279
3300.211
3334.237
3396.998
3493.330
3509.153
3668.238
3670.218
3868.826
3868.969
4095.786
4095.789
4347.409
4347.409
4622.221
4622.256
4919.073
4919.073
5237.223
5237.223
5576.072
5576.072
5935.256
5935.256
6314.483
6314.483
6713.698
6713.698
7132.751
7132.751
7571.635
7571.635
2802.260
2802.260
3050.657
3050.657
3271.646
3271.881
3463.200
3466.595
3614.113
3638.520
3720.010
3801.480
3826.480
3975.666
3979.411
4173.984

d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
a
a
a
a

d
d
d
d
d
d
d
d
d
d
d

C 2001 Elsevier Science

(010))
d
d
d
d
d
a
a
a
a

d
d

d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d

7708.295
8128.485
8128.485
8568.592
8568.592
3930.315
3930.315
4191.256
4191.291
4418.476
4419.190
4609.095
4617.121
4749.217
4793.553
4853.290
4967.941
4981.591
5160.756
5162.347
5380.715
5380.851
5627.594
5627.622
5899.252
5899.260
6194.051
6194.016
6510.577
6510.577
6848.113
6848.113
7206.073
7206.073
7583.951
7583.951
7981.602
7981.602
8398.940
8398.940
8835.273
8835.273
9292.624
9292.624
4187.166
4187.166
4462.397
4462.420
4703.124
4703.542
4908.538
4913.621
5066.114
5099.072
5177.710
5276.814
5298.647
5468.553
5471.580
5686.167

d
d
d
d
d
a
a
a
a

d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d

33

EMISSION SPECTRUM OF HOT HDO

TABLE 2Continued

TABLE 2Continued

Ka

Kc

(000)

(010))

Ka

Kc

(000)

20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21

8
9
9
10
10
11
11
12
12
13
13
14
14
15
15
16
16
17
17
18
18
19
19
20
20
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11
12
12
13
13
14
14
15
15
16
16
17
17

12
12
11
11
10
10
9
9
8
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
21
21
20
20
19
19
18
18
17
17
16
16
15
15
14
14
13
13
12
12
11
11
10
10
9
9
8
8
7
7
6
6
5
5
4

4174.310
4398.724
4398.751
4648.370
4648.370
4921.249
4921.298
5216.184
5216.183
5532.262
5532.262
5868.922
5868.922
6225.765
6225.765
6602.449
6602.449
6998.872
6998.872
7415.020
7415.020
7850.792
7850.792
8306.233
8306.233
3073.522
3073.522
3334.489
3334.489
3567.588
3567.717
3771.939
3773.988
3938.799
3955.624
4057.068
4123.665
4160.851
4297.931
4304.654
4494.019
4494.722
4716.394
4716.430
4963.892
4963.865
5234.753
5234.811
5527.668
5527.638
5841.622
5841.622
6175.990
6175.990
6530.456
6530.456
6904.470
6904.470
7298.083
7298.083

5686.451
5930.817
5930.876
6200.454
6200.486
6492.761
6493.259
6807.780
6807.780
7143.146
7143.146
7498.846
7498.846
7874.153
7874.153
8269.020
8269.020
8683.378
8683.378
9117.080
9117.080

21
21
21
21
21
21
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
23
23
23
23
23
23
23
23
23
23
23

18
18
19
19
20
20
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11
12
12
13
13
14
14
15
15
16
16
17
17
18
18
19
19
20
20
21
21
0
1
1
2
2
3
3
4
4
5
5

4
3
3
2
2
1
22
22
21
21
20
20
19
19
18
18
17
17
16
16
15
15
14
14
13
13
12
12
11
11
10
10
9
9
8
8
7
7
6
6
5
5
4
4
3
3
2
2
1
23
23
22
22
21
21
20
20
19
19
18

7711.152
7711.152
8143.730
8143.730
8595.807
8595.807
3356.925
3356.925
3630.374
3630.374
3875.405
3875.470
4092.042
4093.277
4273.922
4285.128
4406.977
4459.463
4511.727
4634.736
4646.194
4828.835
4830.210
5048.678
5048.896
5293.884
5293.801
5562.592
5562.690
5853.317
5853.387
6165.160
6165.161
6497.213
6497.213
6849.654
6849.654
7220.487
7220.487
7611.189
7611.189
8021.164
8021.164
8450.371
8450.371

d
d

d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d

d
d
d
d
d
d
d
d
d
d

4456.096
4456.096
4745.621
4745.655
4999.574
4999.845
5219.015
5222.179
5393.863
5417.441
5516.611
5599.847
5632.839
5791.130
5796.611
6006.537
6007.002
6248.737
6248.812
6516.115
6516.170
6806.751
6806.916
7119.314
7119.294
7452.436
7452.436
7805.845
7805.845
8178.497
8178.497
8570.474
8570.474
8981.761
8981.761

d
d
d
d
d
d
d
d
d
d
d
d
d
d

d
d

d
d
d
d
d
d
d
d
d
d

C 2001 Elsevier Science

9366.836
9366.836
3652.398
3652.398
3938.265
3938.265
4195.052
4195.107
4423.568
4424.292
4619.446
4626.722
4768.576

(010))
d
d
d
d
d
d
d
d
d
d

d
d
d
d
d
d
d
d
d
d
d
d
d
d

d
d
d
d
d
d

9412.196
9412.196
9862.164
9862.164

d
d
d
d

4737.062
4737.062
5040.850
5040.747
5307.810
5308.036
5540.636
5542.561
5731.948
5748.263
5868.944
5936.508
5983.725
6128.461
6137.661
6341.365
6342.450
6581.137
6581.252
6845.751
6845.827
7134.677
7134.862
7445.060
7445.120
7775.878
7775.878
8127.124
8127.271
8496.873
8496.873
8885.837
8885.837
9294.019
9294.019
9721.085
9721.085

d
d

10632.566
10632.566

d
d

5030.012
5030.012
5347.989
5348.017
5627.771
5627.642
5873.463
5874.594
6080.213
6091.177
6233.324

d
d

d
d

d
d
d
d
d
d
d
d

34

PAREKUNNEL ET AL.

TABLE 2Continued

TABLE 2Continued

Ka

Kc

(000)

(010))

Ka

Kc

(000)

23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24

6
6
7
7
8
8
9
9
10
10
11
11
12
12
13
13
14
14
15
15
16
16
17
17
18
18
20
20
21
21
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11
12
12
13
13
14
14
15

18
17
17
16
16
15
15
14
14
13
13
12
12
11
11
10
10
9
9
8
8
7
7
6
6
5
4
3
3
2
24
24
23
23
22
22
21
21
20
20
19
19
18
18
17
17
16
16
15
15
14
14
13
13
12
12
11
11
10
10

4808.411
4878.296
4985.818
5004.291
5178.253
5180.822
5395.498
5395.765
5638.233
5638.455
5904.704
5904.816
6193.249
6193.282
6502.823
6502.860
6832.444
6832.444
7181.439
7181.439
7550.428
7550.428
7938.136
7938.136
8344.912
8344.912
9213.862
9213.862

6286.414
6350.622
6479.813
6494.921
6690.747
6692.876
6927.921
6928.185
7190.978
7191.122
7476.729
7476.997
7784.920
7784.816
8113.377
8113.337
8463.318
8463.421
8829.215
8829.215
9216.976
9216.976
9620.066
9620.066

24
24
24
24
24
24
24
24
24
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
26
26
26
26
26
26
26
26
26
26
26
26
26
26
26
26

15
16
16
17
17
18
18
19
19
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11
12
12
13
13
14
14
15
15
16
16
17
17
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8

9
9
8
8
7
7
6
6
5
25
25
24
24
23
23
22
22
21
21
20
20
19
19
18
18
17
17
16
16
15
15
14
14
13
13
12
12
11
11
10
10
9
9
8
26
26
25
25
24
24
23
23
22
22
21
21
20
20
19
19

7528.079
7894.226
7894.226
8278.846
8278.846
8682.347
8682.347
9104.665
9104.665
4279.321
4279.320
4589.759
4589.762
4869.569
4869.569
5120.929
5121.170
5342.191
5345.054
5523.459
5543.933

3959.891
3959.891
4258.076
4258.081
4526.455
4526.485
4766.537
4766.968
4975.506
4980.108
5140.984
5170.049
5259.364
5350.860
5379.016
5542.104
5546.741
5756.701
5757.217
5996.865
5996.999
6260.933
6261.034
6547.199
6547.251
6854.498
6854.372
7181.611
7181.617
7528.079

d
d
d
d
d
d
d
d
d
d
d
d

11429.137
11429.137
5334.785
5334.863
5667.067
5667.101
5959.349
5959.423
6217.584
6218.237
6438.692
6445.890
6608.881
6649.089
6732.807
6845.050
6868.741
7053.298
7058.249
7288.980
7289.506
7549.341
7549.555
7832.690
7833.146
8138.808
8138.644
8464.738
8464.716
8806.790
8807.590
9175.441

d
d
d
d
d
d

d
d

C 2001 Elsevier Science

(010))
d
d
d
d
d
d
d
d
d

d
d

5729.143
5770.084
5920.136
5928.097
6132.213
6133.163
6369.613
6369.775
6631.188
6631.319
6915.017
6915.132

7544.584
7544.584

8251.751
8251.683
8633.244
8633.244
4610.681
4610.695
4933.236
4933.225
5224.284
5224.285
5486.675
5486.816
5719.617
5721.398
5915.732
5929.711
6060.513
6120.538
6177.083
6311.976

9175.441

9558.701

5651.141
5651.555
5997.975
5998.035
6302.605
6302.679
6572.948
6573.279
6807.427
6812.044
6994.663
7024.132
7128.614
7224.271
7258.859
7433.214
7438.777
7665.121
7921.830

d
d

8202.490
8203.137
8506.605
8506.267
8829.914
8829.871
9170.915
9171.232
9535.491
9535.481
9915.396
9915.396

d
d

d
d
5980.020
5980.020
6340.678
6340.881
6657.395
6657.482
6939.529
6939.677
7186.554
7189.433
7410.985
7537.166

7824.851

d
d

35

EMISSION SPECTRUM OF HOT HDO

TABLE 2Continued

TABLE 2Continued

Ka

Kc

(000)

(010))

26
26
26
26
26
26
26
26
26
26
26
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
28
28
28
28
28
28
28
28
28
28
28
28
28
28
28
29
29
29
29
29
29

8
9
9
10
10
11
11
12
12
13
13
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
9
9
10
10
11
11
12
12
13
13
14
14
0
1
1
2
2
3
3
4
4
5
5
6
6
7
8
0
1
1
2
2
3

18
18
17
17
16
16
15
15
14
14
13
27
27
26
26
25
25
24
24
23
23
22
22
21
21
20
19
19
18
18
17
17
16
16
15
15
14
14
13
28
28
27
27
26
26
25
25
24
24
23
23
22
22
21
29
29
28
28
27
27

6325.097
6521.824
6523.580
6756.370
6756.649
7015.293
7015.471
7296.663
7296.823
7599.052
7599.055
4953.766
4953.766
5288.457
5288.452
5590.581
5590.566
5863.717
5863.808
6107.851
6108.923
6317.700
6327.007
6478.228
6524.436
6598.915
6737.922
6925.321
6928.513
7156.989
7157.462
7413.162
7413.377
7691.922
7692.139
7992.035
7991.856
8311.383
8311.380
5308.590
5308.590
5655.240
5655.231
5968.269
5968.269
6251.986
6252.026
6506.866
6507.530
6729.440
6735.531
6906.086
6940.441
7136.548
5675.066
5675.066

7834.413
8052.206

6357.327
6357.327

d
d

d
d

d
d
d
d

d
d

d
d

d
d

6320.332
6320.332
6694.723
6695.133
7023.628
7023.788
7317.341
7317.265
7575.770
7577.429

d
d

Ka

Kc

(000)

29
29
29
29
29
29
30
30
30
30
30
30
30
30

3
4
4
5
5
6
0
1
2
3
3
4
4
5

26
26
25
25
24
24
30
30
28
28
27
27
26
26

6651.376
6651.410
6916.640
6917.028
7151.108
7155.008

(010))

7411.070
7411.070
6757.643
6757.643
7061.823
7061.832
7337.012
7337.253

d
d

d
d

TABLE 3
Experimental Term Values in cm1 for the (020) and
(030) Vibrational States of HDO

6672.286
6672.286
7061.489
7061.055
7401.298
7401.602
7706.042
7706.222
7976.087
7976.999

d
d

7035.849
7035.849
7438.591
7438.726
7790.198
7791.556

d
d

Ka

Kc

(020)

6
6
6
6
6
6
6
6
6
6
6
6
6
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
8
8
8

0
1
1
2
2
3
3
4
4
5
5
6
6
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
0
1
1

6
6
5
5
4
4
3
3
2
2
1
1
0
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
8
8
7

3089.126
3092.811
3154.965
3186.626
3206.336
3291.072
3292.976
3425.685
3425.748
3594.668
3594.669
3795.879
3795.879
3185.579
3187.760
3268.346
3292.830
3324.490
3401.218
3405.847
3535.818
3536.047
3704.195
3704.199
3904.897
3904.898
4135.476
4135.476
3294.197
3295.443
3395.168

From Toth (18).

From Toth (21).
c Level reassigned from Toth (21).
d Levels treated as degenerate.
b

C 2001 Elsevier Science

(030)
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a

4451.759
4456.083
4519.117
4555.954
4575.059
4672.403
4674.109
4825.009
4825.057
5015.533
5015.534
5240.158
5240.158
4548.066
4550.724
4632.882
4662.303
4693.313
4782.865
4786.940
4935.425
4935.606
5125.396
5125.400
5349.536
5349.536
5604.348
5604.348
4656.481
4658.062
4760.389

b
b
b
b
b
b
b
b
b
b
b
d
d
b
b
b
b
b
b
b
b
b
b
d
d
d
d
b
b
b

36

PAREKUNNEL ET AL.

TABLE 3Continued
J

Ka

Kc

(020)

8
8
8
8
8
8
8
8
8
8
8
8
8
8
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
11
11
11
11
11
11

2
2
3
3
4
4
5
5
6
6
7
7
8
8
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
0
1
1
2
2
3

7
6
6
5
5
4
4
3
3
2
2
1
1
0
9
9
8
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
10
10
9
9
8
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
11
11
10
10
9
9

3413.012
3459.535
3526.894
3536.354
3661.860
3662.525
3829.486
3829.508
4029.533
4029.533
4259.517
4259.517
4517.274
4517.274
3415.036
3415.732
3534.570
3546.853
3610.681
3667.776
3684.868
3803.790
3805.449
3970.574
3970.645
4169.791
4169.790
4399.060
4399.060
4656.109
4656.109
4939.118
4939.118
3548.148
3548.530
3685.981
3694.020
3777.003
3823.522
3851.399
3961.528
3965.184
4127.477
4127.688
4325.684
4325.686
4554.094
4554.094
4810.320
4810.320
5092.462
5092.462
5399.039
5399.039
3693.560
3693.768
3849.171
3854.222
3957.464
3993.756

TABLE 3Continued
(030)

a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
d
d
d
d
a
a
a
a
a
a
a
a
a
a
a
a
d
d
d
d
d
d
d
d
a
a
a
a
a
a

4782.755
4828.795
4908.896
4917.294
5061.768
5062.297
5251.033
5251.051
5474.554
5474.554
5728.796
5728.796
6010.901
6010.901
4777.040
4777.960
4900.782
4916.961
4980.608
5050.239
5065.595
5204.030
5205.350
5392.467
5392.524
5615.242
5615.242
5868.765
5868.765
6150.151
6150.151
6457.181
6457.181
4909.788
4910.315
5053.412
5064.591
5148.026
5206.573
5231.952
5362.130
5365.038
5549.718
5549.876
5771.521
5771.521
6024.234
6024.234
6304.800
6304.800
6610.936
6610.936
6940.950
6940.951
5054.751
5055.050
5217.919
5225.344
5330.063
5377.525

b
b
b
b

b
b
d
d
d
d
d
d
b
b
b
b
b
b
b
b
c
c

d
d
d
d
d
d
b
b
b
b
b

d
d
d
d
d
d
d
d
d
d
b
b
b
b

Ka

Kc

(020)

11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13

3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11
12
12
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9

8
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
12
12
11
11
10
10
9
9
8
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
13
13
12
12
11
11
10
10
9
9
8
8
7
7
6
6
5
5

4035.537
4134.914
4142.173
4300.205
4300.743
4497.212
4497.234
4724.597
4724.597
4979.884
4979.884
5261.060
5261.060
5566.586
5566.586
5895.293
5895.293
3851.280
3851.391
4024.142
4027.219
4151.015
4177.912
4236.551
4323.706
4336.861
4488.727
4489.966
4684.378
4684.447
4910.560
4910.562
5164.766
5164.766
5444.871
5444.871
5749.250
5749.250
6076.692
6076.692
6426.289
6426.289
4021.296
4021.354
4210.990
4212.824
4356.753
4375.881
4453.505
4527.591
4549.511
4692.963
4695.583
4887.169
4887.336
5111.967
5111.965
5364.940
5364.962
5643.861

C 2001 Elsevier Science

(030)
a
a
a

d
d
d
d
d
d
d
d
d
d
a
a
a
a
a
a
a

d
d
d
d
d
d
d
d
d
d
a
a
a
a
a
a

5416.346
5535.919
5541.765
5722.771
5723.160
5943.435
5943.453
6195.163
6195.164
6474.798
6474.798
6779.960
6779.960
7108.852
7108.852
7460.204
7460.204
5211.937
5212.106
5394.190
5398.980
5525.707
5562.713
5617.859
5725.215
5735.733
5911.820
5912.591
6130.957
6130.998
6381.545
6381.547
6660.119
6660.124
6964.188
6964.189
7291.935
7291.935
7641.921
7641.921
8013.230
8013.230
5381.322
5381.423
5582.254
5585.279
5734.016
5761.719
5835.820
5929.705
5948.035
6116.181
6118.087
6334.060
6334.173
6583.309
6583.317
6860.666
6860.702
7163.574

d
d
d
d
d
d
b
b

d
d
d
d
d
d
b
b

37

EMISSION SPECTRUM OF HOT HDO

TABLE 3Continued
J

Ka

Kc

(020)

13
13
13
13
13
13
13
13
13
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15

9
10
10
11
11
12
12
13
13
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11
12
12
13
13
14
14
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11

4
4
3
3
2
2
1
1
0
14
14
13
13
12
12
11
11
10
10
9
9
8
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
15
15
14
14
13
13
12
12
11
11
10
10
9
9
8
8
7
7
6
6
5
5
4

5643.861
5946.981
5946.981
6273.070
6273.070
6621.146
6621.146
6990.499
6990.499
4203.589
4203.613
4409.821
4410.895
4574.064
4587.080
4685.335
4746.182
4780.039
4912.775
4917.900
5105.553
5105.951
5328.760
5328.778
5580.359
5580.361
5857.987
5857.987
6159.757
6159.741
6484.356
6484.356
6830.839
6830.839
7198.305
7198.305
7587.022
7587.022
4398.133
4398.144
4620.707
4621.328
4802.663
4811.219
4930.919
4979.068
5027.996
5147.962
5157.261
5339.468
5340.341
5560.912
5560.968
5810.921
5810.935
6087.162
6087.161
6387.476
6387.476
6710.528
6710.528

TABLE 3Continued
(030)

d
d
d
d
d
d
d
d
d
a
a
a
a

d
d

d
d
d
d
d
d
d
d
a
a
a
a

d
d

7163.574
7490.065
7490.065
7838.575
7838.575
8208.206
8208.206
8599.229
8599.229
5562.927
5562.982
5782.226
5784.103
5954.206
5974.167
6069.247
6149.058
6177.898
6336.283
6340.039
6552.689
6552.949
6800.405
6800.438
7076.506
7076.482
7378.061
7378.061
7703.206
7703.206
8050.141
8050.141
8417.949
8417.949
8807.787
8807.787
9215.047
9215.047
5756.723
5756.685
5994.169
5995.322
6185.804
6199.696
6317.066
6382.887
6425.431
6571.788
6578.695
6786.789
6787.367
7032.879
7032.852
7307.404
7307.400
7607.569
7607.554
7931.301
7931.301
8276.553
8276.553

d
d
d
d
d
d
d
d
d

d
d
d
d
d
d
d
d
d
d
d
d

d
d
d
d

Ka

Kc

(020)

15
15
15
15
15
15
15
15
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17

12
12
13
13
14
14
15
15
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
11
12
12
13
13
14
14
15
15
16
16
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10

4
3
3
2
2
1
1
0
16
16
15
15
14
14
13
13
12
12
11
11
10
10
9
9
8
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
17
17
16
16
15
15
14
14
13
13
12
12
11
11
10
10
9
9
8
8

7055.295
7055.295
7420.797
7420.797
7807.703
7807.703
8213.975
8213.975
4604.889
4604.895
4843.687
4844.048
5042.533
5047.993
5189.148
5225.805
5292.562
5398.267
5414.029
5588.862
5590.624
5808.391
5808.515
6056.728
6056.729
6331.399
6331.338
6629.985
6630.093
6951.509
6951.509
7294.505
7294.505
7657.897
7657.897
8042.931
8042.931
8446.768
8446.768
8870.284
8870.284
4823.826
4823.826
5078.784
5079.003
5293.768
5297.188
5459.125
5485.970
5572.703
5663.264
5688.369
5853.563
5856.961
6071.108
6071.366
6317.517
6317.555
6590.166
6590.521
6887.482

C 2001 Elsevier Science

(030)
d
d
d
d
d
d
d
d
a
a

8642.442
8642.442
9030.968
9030.968
9435.691
9435.691
9860.164
9860.164
5962.595
5962.616
6218.156
6218.862
6428.599
6437.996
6578.216
6630.897
6690.038
6822.431
6834.354
7036.262
7037.456

d
d
d
d
d
d
d
d

7280.540

8174.291
8174.284
d
d
d
d
d
d
d
d
d
d
d
d
d
d

8881.623
8881.623
9268.805
9268.725
9670.878
9670.878
10092.855
10092.855

d
d

6180.624
6180.624
6454.221
6454.638
6682.573
6688.802
6851.657
6892.335
6970.837
7087.895
7107.258

d
d

d
d
d
d

38

PAREKUNNEL ET AL.

TABLE 3Continued
J

Ka

Kc

(020)

17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
19
19
19
19
19
19
19
19
19
19

10
11
11
12
12
13
13
14
14
15
15
16
16
17
17
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
11
12
12
13
13
14
14
15
15
16
16
17
17
18
18
0
1
1
2
2
3
3
4
4
5

7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
18
18
17
17
16
16
15
15
14
14
13
13
12
12
11
11
10
10
9
9
8
7
7
6
6
5
5
4
4
3
3
2
2
1
1
0
19
19
18
18
17
17
16
16
15
15

6887.748
7207.185
7207.183
7548.568
7548.568
7909.580
7909.580
8292.651
8292.651
8693.918
8693.918
9114.763
9114.763
9553.977
9553.977
5054.907
5054.907
5325.981
5326.073
5556.514
5558.617
5740.213
5759.595
5867.250
5942.614
5980.165
6133.408
6139.572
6349.142
6349.565
6593.183
6593.387
6864.234
6864.827
7159.668
7159.394
7477.528
7816.054
7816.055
8175.745
8175.745
8556.839
8556.839
8955.350
8955.350
9373.426
9373.426
9809.778
9809.778
10258.304
10258.304
5298.092
5298.092
5585.278
5585.329
5830.849
5832.122
6032.024
6044.858
6176.016
6235.871

TABLE 3Continued
(030)

8773.701
8773.684
d
d
d
d
d
d
d
d
d
d
d
d
d
d

d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d

6410.733
6410.733
6702.406
6702.645
6947.844
6951.889
7136.553
7167.029
7266.800

6652.504
6652.646
6962.716
6962.827
7224.509
7227.091
7432.226
7454.531
7576.713

d
d

Ka

Kc

(020)

19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
21
22
22
22
22
22
22
22
22

5
6
6
7
7
8
8
9
9
10
10
11
11
12
12
13
13
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
9
9
0
1
1
2
2
3
3
4
4
5
6
6
7
7
8
8
10
10
0
1
1
2
2
3
3
4

14
14
13
13
12
12
11
11
10
10
9
9
8
8
7
7
6
20
20
19
19
18
18
17
17
16
16
15
15
14
14
13
13
12
11
21
21
20
20
19
19
18
18
17
17
16
15
15
14
14
13
12
11
22
22
21
21
20
20
19
19

6288.926
6428.113
6438.720
6641.838
6643.079
6884.063
6884.128
7152.897
7152.522
7446.587
7446.117
7762.375
7762.359
8099.137
8099.137
8456.368
8456.368
5553.322
5553.322
5856.631
5856.645
6116.857
6117.619
6334.436
6342.986
6496.337
6542.561
6613.810
6737.434
6754.659
6950.001
6951.936
7189.485
7456.101
7455.924
5820.577
5820.616
6140.014
6140.037
6414.528
6414.949
6647.595
6653.128
6827.262
6862.266
7060.912
7087.217
7272.515
7276.268
7508.776
7510.086
8064.452
8063.861
6099.713
6099.802
6435.418
6435.483
6723.891
6724.127
6971.579
6975.122

C 2001 Elsevier Science

(030)

a
d
d
d
d

6906.757
6906.824
7235.211
7235.160
7512.665
7514.248
7738.131
7754.482
7899.724

7172.861
7172.929
7519.627
7812.473
7813.166

7450.882
7451.331
7816.239
7815.555

39

EMISSION SPECTRUM OF HOT HDO

TABLE 3Continued
J

Ka

Kc

(020)

22
22
22
22
22
23
23
23
23
23
23
23
23
24
24
24
24
24
24
24
24
24
25
25
25
25
25
25
25
26
26
26
26
27
27

4
5
5
6
6
0
1
1
2
2
3
3
4
0
1
1
2
2
3
3
4
4
0
1
1
2
2
3
3
0
1
1
2
0
1

18
18
17
17
16
23
23
22
22
21
21
20
20
24
24
23
23
22
22
21
21
20
25
25
24
24
23
23
22
26
26
25
25
27
27

7169.329
7194.425
7308.237
7398.144
7436.726
6390.891
6390.998
6742.804
6742.966
7044.892
7044.949
7306.531
7308.736
6693.846
6693.943
7062.126
7063.575
7377.377
7377.530
7652.538
7653.801
7881.869
7008.773
7008.797
7392.866
7393.400
7721.393
7721.804
8009.664
7335.478
7335.497
7736.133
7736.662
7673.981
7674.006

TABLE 4Continued
(030)

7740.686
7740.803

8042.550
8042.658

d
d

TABLE 4
Experimental Term Values for the (040) Vibrational
State of HDO
J

Ka

Kc

E / cm1

1
1
2
2
3
3
3
3
3
3
3
4
4
4
4
5

0
1
0
1
0
1
1
2
2
3
3
0
1
2
2
0

1
0
2
1
3
3
2
2
1
1
0
4
4
3
2
5

5435.6068
5465.0623
5466.4376
5499.5585
5511.8399
5530.7079
5551.0726
5620.0923
5621.7228
5802.9254
5802.9551
5571.0447
5585.5093
5681.7361
5686.4474
5643.1421

Ka

Kc

E / cm1

5
5
5
5
6
6
6
6
7
7
7
7
7
7
7
8
8
8
8
8
9
9
9
9
9
9
9
9
9
9
10
10
10
10
10
10
11
11
11
11
11
11
11
11
12
12
12
12
13
13

1
1
2
2
0
1
1
2
0
1
1
2
3
3
4
0
1
1
2
2
0
1
2
2
3
0
1
2
2
3
0
1
1
2
4
4
1
1
2
4
1
1
2
4
0
1
0
1
0
1

5
4
4
3
6
6
5
5
7
7
6
5
5
4
4
8
8
7
7
6
9
9
8
7
7
9
9
8
7
7
10
10
9
8
7
6
11
10
10
8
11
10
10
8
12
12
12
12
13
13

5653.5189
5703.6235
5758.3228
5768.6395
5727.4602
5734.4833
5803.5002
5849.5472
5823.6422
5828.1982
5918.0485
5985.9790
6149.7993
6153.3642
6320.5506
5931.5867
5934.4373
6046.2411
6074.5291
6120.4486
6051.3254
6053.0712
6207.5327
6271.1832
6417.2246
6051.3254
6053.0712
6207.5327
6271.1832
6417.2246
6182.9611
6184.0147
6339.7061
6504.9100
6747.7909
6749.9688
6327.1599
6503.6295
6583.8419
6921.7836
6327.1599
6503.6295
6583.8419
6921.7836
6482.0818
6482.4608
6482.0818
6482.4608
6649.6576
6649.8965

4. CONCLUSIONS

We present the first hot emission spectrum of HDO. This

spectrum is very dense since it contains many lines belong to
H2 O and D2 O as well as HDO. HDO lines have been identified by comparison with other hot emission spectra. The HDO

C 2001 Elsevier Science

40

PAREKUNNEL ET AL.

transitions have been analyzed resulting in the assignment of

many hot pure rotational transitions, bending hot bands linking
states up to the previously unobserved (040) bending state, and
vibrational difference bands.
ACKNOWLEDGMENTS
We thank A. Rudolph for assistance with the measurements. This work was
supported by the Natural Sciences and Engineering Research Council of Canada
(NSERC). Some support was also provided by the NASA Laboratory Astrophysics Program, the UK Engineering and Science Research Council, and the
Royal Society and the Russian Fund for Fundamental Studies under Grants
N 01-02-06411 and N 00-02-16604.

REFERENCES
1. J. Tennyson, N. F. Zobov, R. Williamson, O. L. Polyansky, and P. F.
Bernath, J. Phys. Chem. Ref. Data, in press.
2. M. Carleer, A. Jenouvrier, A.-C. Vandaele, P. F. Bernath, M. F. Merienne,
R. Colin, N. F. Zobov, O. L. Polyansky, J. Tennyson, and V. A. Savin,
J. Chem. Phys. 111, 24442450 (1999).
3. N. F. Zobov, D. Belmiloud, O. L. Polyansky, J. Tennyson, S. V. Shirin,
M. Carleer, A.-C. Vandaele, P. F. Bernath, M. F. Merienne, and R. Colin,
J. Chem. Phys. 113, 15461552 (2000).
4. O. L. Polyansky, N. F. Zobov, S. Viti, J. Tennyson, P. F. Bernath, and
L. Wallace, J. Mol. Spectrosc. 186, 422447 (1997).
5. N. F. Zobov, O. L. Polyansky, J. Tennyson, J. A. Lotoski, P. Colarusso,
K.-Q. Zhang, and P. F. Bernath, J. Mol. Spectrosc. 193, 118136 (1999).
6. N. F. Zobov, O. L. Polyansky, J. Tennyson, S. V. Shirin, R. Nassar, T.
Hirao, T. Imajo, P. F. Bernath, and L. Wallace, Astrophys. J. 530, 994998
(2000).
7. R. Lanquetin, L. H. Coudert, and C. Camy-Peyret, J. Mol. Spectrosc. 206,
83103 (2001).
8. L. Wallace, P. Bernath, W. Livingston, K. Hinkle, J. Busler, B. Guo, and
K.-Q. Zhang, Science 268, 11551158 (1995).
9. H. Partridge and D. W. Schwenke, J. Chem. Phys. 106, 46184639 (1997).
10. O. L. Polyansky, N. F. Zobov, S. Viti, J. Tennyson, P. F. Bernath, and
L. Wallace, Science 277, 348356 (1997).
11. F. W. Irion, E. J. Moyer, M. R. Gunson, C. P. Rinsland, Y. L. Yung,
H. A. Michelsen, R. J. Salawitch, A. Y. Chang, M. J. Newchurch, M. M.
Abbas, M. C. Abrams, and R. Zander, Geophys. Res. Lett. 23, 23812384
(1996).
12. R. I. Epstein, J. M. Latimer, and D. N. Schramm, Nature 263, 198207
(1976).
13. R. Meier, T. C. Owen, H. E. Mathews, D. C. Jewitt, D. Bockelee-Morvan,
N. Biver, J. Crovisier, and D. Gautier, Science 279, 842844 (1998).

14. D. W. Schwenke, J. Phys. Chem. A 105, 23522360 (2001).

15. R. L. Vander Wal, J. L. Scott, F. F. Crim, K. Weide, and R. Schinke,
J. Chem. Phys. 94, 35483555 (1991).
16. W. S. Benedict, N. Gailar, and E. K. Plyler, J. Chem. Phys. 24, 11391165
(1956).
17. N. Papineau, C. Camy-Peyret, J.-M. Flaud, and G. Guelachvili, J. Mol.
Spectrosc. 92, 451468 (1982).
18. R. A. Toth, J. Mol. Spectrosc. 195, 7397 (1999).
19. R. A. Toth, J. Mol. Spectrosc. 162, 2040 (1993).
20. R. A. Toth, V. D. Gupta, and J. W. Brault, Appl. Opt. 21, 33373347 (1982).
21. R. A. Toth and J. W. Brault, Appl. Opt. 22, 908926 (1983).
22. R. A. Toth, J. Mol. Spectrosc. 186, 276292 (1997).
23. R. A. Toth, J. Mol. Spectrosc. 186, 6689 (1997).
24. (R. S. Mulliken), J. Chem. Phys. 23, 19972011 (1955).
25. A. D. Bykov, Yu. S. Makushkin, V. I. Serdyukov, L. N. Sinitsa, O. N.
Ulenikov, and G. A. Ushakova, J. Mol. Spectrosc. 105, 397409 (1984).
26. A. D. Bykov, V. P. Lopasov, Yu. S. Makushkin, L. N. Sinitsa, and
V. E. Zuev, J. Mol. Spectrosc. 94, 127 (1982).
27. S.-M. Hu, O. N. Ulenikov, G. A. Onopenko, E. S. Bekhtereva, S.-G. He,
X.-H. Wang, and Q.-S. Zhu, J. Mol. Spectrosc. 203, 228234 (2000).
28. J. K. Messer, F. C. DeLucia, and P. Helminger, J. Mol. Spectrosc. 105,
139155 (1984).
29. O. I. Baskakov, V. A. Alekseev, E. A. Alekseev, and B. I. Pelevoi,
Opt. Spectrosc. 63, 600601 (1987).
30. J. W. C. Johns, J. Opt. Soc. Am. B 2, 13401354 (1985).
31. R. Paso and V.-M. Horneman, J. Opt. Soc. Am. B 12, 18131838 (1995).
32. O. Naumenko, E. Bertseva, and A. Campargue, J. Mol. Spectrosc. 197,
122132 (1999).
33. O. Naumenko and A. Campargue, J. Mol. Spectrosc. 199, 5972 (2000).
34. E. Bertseva, O. Naumenko, and A. Campargue, J. Mol. Spectrosc. 203,
2836 (2000).
35. A. Campargue, E. Bertseva, and O. Naumenko, J. Mol. Spectrosc. 204,
94105 (2000).
36. O. Naumenko, E. Bertseva, A. Campargue, and D. W. Schwenke,
J. Mol. Spectrosc. 201, 297309 (2000).
37. A. Jenouvrier, M. F. Merienne, M. Carleer, R. Colin, A.-C. Vandaele,
P. F. Bernath, O. L. Polyansky, and J. Tennyson, J. Mol. Spectrosc., in press.
38. S. Hu, H. Lin, S. He, J. Cheng, and Q. Zhu, Phys. Chem. Chem. Phys. 1,
37273730 (1999).
39. A. D. Bykov, V. A. Kapitanov, O. V. Naumenko, T. M. Petrova,
V. I. Serdyukov, and L. N. Sinitsa, J. Mol. Spectrosc. 153, 197207 (1992).
40. O. L. Polyansky, N. F. Zobov, J. Tennyson, J. A. Lotoski, and P. F. Bernath,
J. Mol. Spectrosc. 184, 3550 (1997).
41. R. A. Toth, J. Mol. Spectrosc. 194, 2842 (1999).
42. R. A. Toth, J. Mol. Spectrosc. 190, 379396 (1998).
43. D. W. Schwenke available at http://george.arc.nasa.gov/dschwenke/.
44. O. L. Polyansky, J. Tennyson, and P. F. Bernath, J. Mol. Spectrosc. 186,
213221 (1997).

C 2001 Elsevier Science