G. Herzberg and L. Herzberg, "Rotation-Vibration Spectra of Diatomic and Simple Polyatomic Molecules with Long Absorbing PathsXI. The Spectrum of Carbon Dioxide (Co2) below 1.25μ*," J. Opt. Soc. Am. 43, 1037-1044 (1953)
The spectrum of CO2 in the photographic infrared has been studied with absorbing paths up to 5500 m. Thirteen absorption bands were found of which eleven have been analyzed in detail. One of these is due to C13O2. From the band origins of the C12O2 bands improved values for some of the anharmonic constants of the molecule have been derived.
The study of the rotational structure of the photographic infrared CO2 bands has yielded considerably improved values for the rotational constants. The new values are B000=0.39020 cm−1, α1=+0.00109, α2=−0.00073, α3=+0.00307 cm−1. From these the following equilibrium values of rotational constant, moment of inertia, and internuclear distance are obtained:
By taking account of the effect of Fermi resonance, excellent agreement of the observed B[v] values with those calculated from the αi and Be is obtained.
The l-type doubling in the states 0110, 1113, and 0313 has been determined. The agreement of the splitting constants q with those obtained from theory is satisfactory.
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In the case of polyads only the first member is given although the complete polyad was used in each case.
Reference 11.
From Benedict and Plyler (reference 13).
Table V
Combination differences Δ2F(J) for the ground state (00°0) of CO2.
Only the data from the bands ν1+3ν3, ν1+2ν2+3ν3, 2ν1+3ν3, and 5ν3 have been included in the mean. Data from weak (†) and blended (*) lines have been omitted in the averaging.
Table VI
Rotational constants Bv of CO2.
Level
Bv1v2v3′, observed (cm−1)
Bv1v2v3′, calculated
v1
v2
v3
Individual values
Means of polyads
Monads and means of polyads
Observed-calculated
Individual values of polyads
Observed-calculated
0
00
0
0.39020
0.39020
0 assumed
0
11
0
0.39090
0.39093
−0.00003
0
20
0
0.3906
0.39045
0.39039
+0.00006
0.39059
+0.00001
1
00
0
0.3903
0.39018
+0.00012
0
00
1
0.3872
0.38713
+0.00007
0
20
1
0.38738
0.38728
0.38732
−0.00004
0.38752
−0.00014
1
00
1
0.38717
0.38711
+0.00006
0
40
1
0.38808
0.38735
0.38750
−0.00015
0.38838
−0.00030
1
20
1
0.38649
0.38661
−0.00015
2
00
1
0.38749
0.38747
+0.00002
0
51
1
0.38867
0.38823
…
0.38900
−0.00033
1
31
1
0.38747
0.38765
−0.00018
2
11
1
…
0.38799
…
0
60
1
0.38879
0.38749
0.38769
−0.00020
0.38930
−0.00051
1
40
1
0.38663
0.38699
−0.00036
2
20
1
0.38647
0.38650
−0.00003
3
00
1
0.38808
0.38795
+0.00013
0
20
3
0.38150
0.38115
0.38118
−0.00003
0.38139
+0.00011
1
00
3
0.38080
0.38096
−0.00016
0
31
3
0.38222
0.38194
0.38191
+0.00003
0.38215
+0.00007
1
11
3
0.38165
0.38166
−0.00001
0
40
3
0.38231
0.38135
0.38136
−0.00001
0.38224
+0.00007
1
20
3
0.38047
0.38047
+0.00000
2
00
3
0.37127
0.38137
−0.00010
0
00
5
0.37485
0.37485
0 assumed
0
20
5
0.3756
0.37506
0.37504
+0.00002
0.37525
+0.00035
0
00
5
0.37452
0.37482
−0.00030
Table VII
l-type doubling constants for CO2.
Level
q (observed)
v1
v2
v3
Goldberg et al.
Present work
q (calculated)
0
11
0
0.000505
0.00065
0.00061
2
11
1
…
…
0.00116
1
31
1
0.00080
0.00122
0.00109
0
51
1
0.00130
0.00158
0.00141
1
11
3
…
0.00077
0.00086
0
31
3
…
0.00093
0.00097
Tables (7)
Table I
Band heads (λh, νh), band origins (ν0), and assignments of CO2 bands observed in the photographic infrared.
λh (air) (A)
νh (vac) (cm−1)
Estimated intensity
ν0 (vac) (cm−1)
Assignment
12 334.2
8 105.3
2
8 089.06
2ν2+3ν3 (C13O2)
12 262.5
8 152.7
8
8 135.95
3ν2+3ν3−ν2
12 177.3
8 209.75
100
8 192.62
2ν2+3ν3
12 054.93
8 293.09
8
8 276.83
ν1+ν2+3ν3−ν2
12 030.49
8 309.94
100
8 294.01
ν1+3ν3
10 626.70
9 407.69
4
9 389.02
4ν2+3ν3
10 487.61
9 532.33
20
9 517.00
ν1+2ν2+3ν3
10 361.79
9 648.20
8
9 631.38
2ν1+3ν3
8 688.79
11 505.92
1
11 496.43
5ν3
8 735.95
11 443.81
0.05
…
ν2+5ν3−ν2
7 882.83
12 682.31
0.1
12 672.28
2ν2+5ν3
7 820.11
12 784.03
0.3
12 774.73
ν1+5ν3
7 158.2
13 966.2
0.02
…
ν1+2ν2+5ν3
Table II
Wave numbers of the lines in the CO2 bands (νvac, cm−1).a
2ν2+3ν3
ν1+3ν3
4ν2+3ν3
ν0=8192.62
ν0=8294.01
ν0=9389.02
J
R(J)
P(J)
R(J)
P(J)
R(J)
P(J)
0
8193.390
8294.773
2
94.847
8191.031
96.237
8292.450
9391.246
9387.431
4
96.254
89.377
97.637
90.789
92.642
85.795
6
97.586
87.665
98.952
89.055
94.037
84.107
8
98.852
85.894
8300.196
87.234
95.320
82.351
10
8200.030
84.022
01.348
85.373
96.584
80.507
12
01.170
82.098
02.442
83.419
97.731
78.611
14
02.235
80.125
03.449
81.381
98.812
76.674
16
03.214
78.048
04.386
79.275
99.879
74.659
18
04.140
75.918
05.257
77.101
9400.840
72.581
20
04.992
73.710
06.051
74.835
01.756
70.433
22
05.764
71.415
06.770
72.518
02.622
68.210
24
06.471
69.064
07.403
70.092
03.428
65.968
26
07.096
66.671
07.949
67.625
04.151
63.596
28
07.663
64.204
08.471
65.062
04.771
61.206
30
08.146
61.635
08.883
62.434
05.377
58.758
32
08.594
59.010
09.182†
59.742
05.881
56.234
34
08.954
56.343
09.466†
56.964
06.378
53.615
36
53.600
54.104
50.960
38
50.721
51.174
48.237†
40
47.839
48.189
42
44.885
45.097
44
41.826
41.975
46
38.736*
38.779
48
35.596
35.470*
50
32.117†
52
28.686†
54
25.193†
ν1+2ν2+3ν3
2ν1+3ν3
5ν3
ν0=9517.00
ν0=9631.38
ν0=11 496.43
J
R(J)
P(J)
R(J)
P(J)
R(J)
P(J)
0
9517.749
9632.104†
11 497.224†
2
19.230
9515.422
33.605†
9629.806†
98.583
11 494.830
4
20.606
13.762
35.022
28.198
99.872
93.126
6
21.916
12.021
36.354
26.477
11 501.038
91.288
8
23.153
10.206
37.601
24.630
02.072
89.329
10
24.299
08.311
38.781
22.763
02.978
87.245
12
25.374
06.349
39.901
20.836
03.768
85.046
14
26.374
04.313
40.955
18.835
04.426
82.711
16
27.276
02.173
41.903
16.756
04.977
80.257
18
28.124
9499.972
42.821
14.589
05.407
77.688
20
28.902
97.694
43.632
12.383
05.697
74.988
22
29.577
95.335
44.383
10.072
72.171
24
30.183
92.922
45.087
07.717
69.228
26
30.714
90.397
45.675
05.292
66.166
28
31.156
87.798
46.219
02.772
62.983
30
31.524
85.126
46.697
00.169
59.672
32
31.824†
82.391
47.098†
9597.576
56.236
34
79.570
94.856
52.690
36
76.661
92.060
49.020
38
73.691
89.200†
45.214
40
70.613
86.329†
41.276
42
67.504
37.250
44
64.307
46
61.011
48
57.628
11 496.945
50
54.226†
52
50.670†
2ν2+5ν3
ν1+5ν3
ν0=12 672.28
ν0=12 774.73
J
R(J)
P(J)
R(J)
P(J)
0
12 775.863
2
76.935
12 773.084
4
12 675.92
12 668.96*
78.195
71.430
6
676.92*
79.318
69.596
8
678.05*
665.17*
80.370
67.603
10
678.87*
663.08
81.238
65.509
12
679.77
661.08*
82.019
63.291
14
680.51
658.71
82.666
60.964
16
681.09
656.28
83.218
58.472
18
681.56
653.80
83.643
55.879
20
681.90
651.17
53.178
22
648.38
50.316
24
47.338
26
44.241
28
41.035
30
37.947
32
34.235
34
30.696
3ν2+3ν3−ν2
ν1+ν2+3ν3−ν2
ν0=8135.95
ν0=8276.83
J
R(J)
P(J)
R(J)
P(J)
0
1
8137.39
2
38.25
8134.55
3
38.74*
33.43
4
39.54
32.70
8273.62
5
40.24
31.87
72.53*
6
40.98
31.03
71.87
7
41.56
30.12
8282.43
70.95
8
42.22
29.10*
70.12*
9
42.81
28.25
83.42*
69.17
10
43.43
27.32
84.20
68.17
11
43.95
26.37
84.75
67.16
12
44.53
25.51
85.40*
66.22
13
44.91*
24.40
85.82
65.09*
14
45.62
23.46
86.36
64.01
15
46.06
22.32
86.79
63.14
16
46.66
21.36
87.29*
62.10
17
47.05
20.31
87.68
61.00
18
47.54
19.24
88.19
59.78*
19
47.85*
18.05
88.58
58.80
20
48.44
17.05
89.07*
57.68
21
48.62
15.85
56.63
22
49.20
14.80
55.38
23
49.43
13.54
54.14*
24
50.03
12.45
53.00
25
11.18
51.69
26
10.08
50.50
27
50.72*
08.68
49.17
28
51.14
07.60
47.84
29
06.22
46.39
30
51.67
45.15*
31
03.51
43.96
32
52.19
02.45*
42.68
33
00.87
41.19
34
8099.74
8239.94
35
98.08
38.39
36
97.05
37.06
37
95.30*
35.49*
38
94.18*
34.23
39
32.13*
40
91.33*
31.21
41
89.35
29.50
42
27.71
An asterisk indicates blended lines. A dagger indicates very faint lines.
Table III
Wave numbers of the lines in the C13O2 band (νvac, cm−1).a
In the case of polyads only the first member is given although the complete polyad was used in each case.
Reference 11.
From Benedict and Plyler (reference 13).
Table V
Combination differences Δ2F(J) for the ground state (00°0) of CO2.
Only the data from the bands ν1+3ν3, ν1+2ν2+3ν3, 2ν1+3ν3, and 5ν3 have been included in the mean. Data from weak (†) and blended (*) lines have been omitted in the averaging.