An analysis of the spectrum of the linear unsymmetric molecule HC12N has been made permitting the determination of the 21 constants necessary for predicting the vibrational frequencies and the 10 constants necessary for predicting the B value for the various vibrational states. To determine these constants new measurements were made on numerous bands in the region of 1–3 μ employing a 5-m vacuum spectrograph. Several instances of Fermi resonance were detected and analyzed. Except for a few bands where additional resonances may be present, the vibrational constants predict the measured values for the band origins of 44 bands within an amount not much greater than the expected experimental error. The rotational constants also predict the B value within the experimental error for 24 bands where data are available.
Bands of HC13N and DC12N were also measured to determine the α values for calculation of the equilibrium moment of inertia. The 101–000 and 1111–0110 bands were used for all three isotopic forms of HCN to determine the Be values in a parallel fashion. From these values the bond length C–H=1.06593±0.00010 A and C–N=1.15313±0.00002 A were determined.
In five different cases in HC12N it was possible to apply the Ritz combination principle to determine the frequency of the 0110 state. By using this value and the rotational constants it was possible to calculate the frequencies of lines in the 0110–000 band. The principle is also applied to HC13N and DC12N.
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Observed and calculated wave numbers of the lines of the HC12N bands. The calculated wave numbers were obtained by use of the rotational constants quoted. It is believed that the wave numbers listed are relatively accurate to 1 part in 107 and absolutely accurate to 1 part in 3×106.
HC12N
HC12N
HC12N
ν
ν1+ν3
ν2+2ν3−ν2
J
Calc R(J) cm−1
Obs cm−1
Calc P(J) cm−1
Obs cm−1
Calc R(J) cm−1
Obs cm−1
Calc P(J) cm−1
Obs cm−1
Obs R(J) cm−1
Obs P(J) cm−1
0
3314.4089
0.410
5396.614
1
17.3236
3308.5169
99.489
0.486
5390.742
0.744
6486.587
2
20.2173
05.5397
5402.324
0.316
87.745
0.744
89.432
6474.807
3
23.0899
02.5418
05.118
0.122
84.708
92.225
71.772
4
25.9415
3299.5233
07.870
0.874
81.630
68.684
5
28.7718
96.4842
10.582
78.512
65.554
6
31.5810
93.4246
13.253
75.354
6500.316
00.425
7
34.3688
90.3446
0.342
15.883
0.889
72.155
0.156
02.934
59.174
03.067
8
37.1352
87.2443
18.472
0.473
68.917
0.920
05.512
55.973
05.662
55.872
9
39.8802
84.1238
21.020
0.022
65.638
08.052
08.222
10
42.6036
80.9830
0.984
23.526
0.526
62.320
49.362
49.234
11
45.3056
0.302
77.8221
0.824
25.991
0.990
58.962
12.994
45.996
13.205
45.856
12
47.9858
74.6412
28.415
55.564
0.563
15.398
42.581
15.629
42.440
13
50.6444
71.4404
30.797
0.800
52.126
17.770
39.135
18.019
38.978
14
53.2813
68.2196
33.138
0.137
48.649
20.092
35.641
20.363
35.473
15
55.8963
64.9790
35.437
45.132
32.111
31.933
16
58.4894
61.7188
37.694
0.693
41.575
24.612
28.543
24.927
28.353
17
61.0606
58.4388
39.910
0.908
37.979
26.810
24.932
27.148
24.733
18
63.6098
0.610
55.1393
42.084
34.344
0.342
28.960
29.319
19
66.1370
51.8203
44.216
0.216
30.670
0.669
17.581
17.372
20
68.6420
48.4819
46.307
0.301
26.956
13.857
13.635
21
71.1249
45.1242
48.355
0.355
23.203
0.201
35.166
10.076
35.593
09.860
22
73.5856
41.7472
50.361
0.359
19.412
0.411
37.147
06.264
37.599
06.032
23
76.0239
38.3511
0.355
52.325
15.581
0.581
02.415
02.177
24
78.4400
34.9359
54.247
0.249
11.711
0.712
6398.517
98.277
25
80.8336
31.5017
0.501
56.127
07.803
42.839
43.364
26
83.2048
28.0486
57.965
0.970
03.856
0.856
27
85.5535
24.5766
0.575
59.760
0.762
5299.870
28
87.8796
0.877
21.0859
0.090
61.513
95.846
0.847
29
90.1831
0.181
17.5766
0.580
63.223
91.783
30
92.4640
14.0487
64.891
87.682
31
94.7222
10.5023
32
96.9576
06.9375
33
99.1702
0.169
03.3544
B′=1.467799
B′=1.457933
B″=1.481828
B′−B″=−0.010420
B′−B″=−0.020286
B′−B″=−0.020705
ν0=3311.473
ν0=5393.698
D″=3.0773×10−6
Q(0)=6480.785
q′=0.007686
q″=0.007488
Table II
Measured doublet separations in vacuum wave numbers of the l-type doublets. It must be remembered that l-type doublets actually represent two distinct π–π bands. In the R branch the πd component occurs at higher frequency than the πc component. However, in the P branch the order of the components is reversed. Hence the separation is designated with a negative sign.
Band
HC12N
HC12N
HC12N
HC13N
DC12N
m
0111–0110
0112–0110
1111–0110
0112–0110
1111–0110
26
0.523
0.260
25
0.444
0.254
24
0.421
23
0.452
22
0.426
21
20
0.346
19
0.329
0.359
0.344
0.351
0.203
18
0.311
0.338
0.335
0.196
17
0.288
0.315
0.186
16
0.284
0.176
15
0.271
0.267
0.162
14
0.249
0.247
0.244
0.154
13
0.231
0.229
0.224
12
0.211
11
0.189
10
0.163
0.171
0.171
9
0.143
0.150
0.148
8
0.128
0.134
7
0.109
0.108
6
0.099
5
4
0.062
−5
−0.073
−6
−7
−0.098
−0.096
−8
−0.112
−0.101
−0.090
−9
−0.112
−10
−0.128
−0.134
−0.119
−0.117
−11
−0.141
−0.128
−0.144
−12
−0.140
−0.155
−0.141
−13
−0.178
−0.157
−0.168
−0.150
−0.168
−14
−0.188
−0.167
−0.176
−0.163
−0.174
−15
−0.178
−0.189
−0.176
−0.194
−16
−0.209
−0.190
−0.198
−0.177
−0.205
−17
−0.224
−0.200
−0.185
−0.220
−18
−0.195
−0.242
−19
−0.209
−0.199
−0.254
−20
−0.250
−0.222
−0.200
−0.277
−21
−0.216
−22
−0.275
−0.232
−23
−0.238
−24
−0.288
−0.240
−25
−0.300
−26
−0.303
−27
−0.319
−28
−0.325
Table III
Wave numbers of Q branches. Only lines which were well resolved and free from other disturbances are listed. The lines marked ‡ were not used for fitting because they show a deviation from the theoretically predicted values. The numbers marked * are calculated from the quoted constants. The numbers are believed to be accurate to ±0.003 cm−1.
ν2+ν3~π−∑
2ν2+ν3−ν2~∑−π
2ν2+ν3−ν2~Δ−π
ν2+2ν3~π−∑
ν1+ν2+ν3
HC12N
HC13N
HC12N
HC13N
HC12N
HC13N
HC12N
HC13N
HC13N
J
Q(J) cm−1
Q(J) cm−1
Q(J) cm−1
Q(J) cm−1
Q(J) cm−1
Q(J) cm−1
Q(J) cm−1
Q(J) cm−1
Q(J) cm−1
0
*4004.169
*3980.781
*3972.351
*3949.920
*3987.099
*3964.346
*7192.755
*7151.648
*6027.368
1
2
72.271
91.378
3
72.211
91.294
4
91.185
51.410
26.982
5
72.041
49.621
91.055
51.294
26.916
6
04.049
80.673
71.919
49.508
86.666
90.895
26.840
7
04.009
80.634
71.776
49.370
86.496
90.706
50.974
26.748
8
03.963
80.592
71.615
49.207
86.315
63.673
90.494
50.764
26.646
9
03.910
80.543
71.429
49.032
63.470
90.255
26.528
10
03.854
80.490
71.218
48.833
85.920
89.989
50.304
26.401
11
03.790
80.431
70.987
85.692
89.697
50.033
26.259
12
03.721
80.368
70.723
85.452
62.842
89.384
49.735
26.107
13
80.299
‡85.203
62.606
89.025
49.417
25.941
14
80.223
‡70.205
‡84.942
62.346
88.656
49.079
25.761
15
03.479
80.144
‡69.863
‡84.668
88.248
48.713
16
03.385
80.058
‡84.386
87.830
17
03.286
18
03.180
‡68.638
‡83.802
19
‡68.163
‡83.503
20
‡83.198
21
79.548
22
79.427
‡82.584
23
02.565
79.302
24
02.413
79.171
25
02.275
79.035
26
02.120
27
78.743
28
78.588
29
78.425
B′−B″=−0.002859
B′−B″=−0.002633
B′−B″=−0.01034
B′−B″=−0.00987
B′−B″=−0.01059
B′−B″=−0.00957
B′−B″=−0.01334
B′−B″=−0.01228
B′−B″=−0.01257
D′−D″=−8.51×10−8
D′−D″=−8.31×10−8
Table IV
HC13N band origins. The band origins have been corrected for l2B and are given in vacuum wave numbers.
Ritz combination principle.
Present measurements.
See reference 16.
Calculated from 00Z–000 series and the 101–000 band.
Table V
Measured wave numbers and rotational constants of some HC13N bands. Only those lines which are free from blends have been measured. These numbers are believed to be accurate to ±0.003 cm−1.
HC13N
HC13N
HC13N
ν1+ν3
2ν3
ν2+2ν3−ν2
J
Obs R(J) cm−1
Obs P(J) cm−1
Obs R(J) cm−1
Obs P(J) cm−1
Obs R(J) cm−1
Obs P(J) cm−1
0
6486.125
1
5340.775
88.934
6480.406
6451.351
2
77.487
54.121
6439.882
3
34.906
94.418
56.859
36.925
4
5357.478
97.102
71.528
59.549
33.921
5
60.131
28.873
68.493
30.878
6
62.734
25.801
6502.349
64.771
27.800
64.879
7
65.312
22.697
04.914
62.305
24.694
8
67.844
19.547
59.160
69.864
21.540
70.013
9
70.339
09.926
55.968
72.358
72.523
10
72.788
13.142
12.373
15.180
15.061
11
09.883
14.782
49.472
11.917
11.789
12
77.580
06.585
17.144
46.168
79.592
08.625
79.816
08.484
13
79.918
03.246
42.820
81.929
05.287
82.173
05.136
14
82.215
21.761
39.439
84.218
01.912
84.486
01.749
15
84.475
5296.468
24.005
36.020
86.477
6398.505
86.761
98.329
16
86.693
93.015
26.213
32.561
95.052
94.876
17
88.873
89.540
90.867
91.566
91.202
91.381
18
91.012
30.507
25.532
93.004
88.049
93.355
87.854
19
82.452
32.596
84.485
84.286
20
95.174
78.857
34.640
18.355
80.886
80.686
21
97.193
36.646
14.708
22
99.175
38.617
11.024
23
5401.119
40.540
24
42.424
03.545
25
6399.752
26
46.077
27
47.840
B′=1.420802
B′=1.420438
B″=1.44319
B′−B″=−0.019186
B′−B″=−0.019550
B′−B″=−0.019149
ν0=5343.657
ν0=6483.286
D″=2.936×10−6
Q(0)=6445.695
q′=0.00734
q″=0.00713
Table VI
Wave numbers and rotational constants of some DC12N bands.
DC12N
DC12N
ν1+ν3
ν1+ν2+ν3−ν2
J
Calc R(J) cm−1
Obs cm−1
Calc P(J) cm−1
Obs cm−1
Obs R(J) cm−1
Obs P(J) cm−1
0
4525.656
4525.655
1
28.005
28.004
4520.858
4520.856
2
30.321
30.320
18.410
18.409
3
32.603
32.603
15.928
15.928
4519.799
4
34.852
34.852
13.413
13.413
22.061
5
37.067
10.865
10.862
24.280
4497.970
6
39.249
08.284
08.282
26.471
95.388
7
41.397
05.671
05.669
28.636
92.764
8
43.513
43.516
03.025
30.752
90.159
90.069
9
45.594
45.596
00.345
00.344
87.489
87.377
10
47.642
47.644
4497.632
4497.632
84.770
84.653
11
49.656
49.658
94.887
94.890
82.040
81.896
12
51.636
51.637
92.110
92.112
13
53.582
53.582
89.299
89.298
40.820
76.461
40.975
76.293
14
55.495
55.497
86.457
86.457
42.746
73.610
42.908
73.435
15
57.374
57.372
83.581
83.581
44.630
70.746
44.806
70.552
16
59.219
59.219
80.674
80.672
46.486
67.840
46.672
67.635
17
61.030
61.029
77.733
77.735
48.310
64.905
48.506
64.685
18
62.808
62.808
74.761
74.760
50.099
61.943
50.303
61.701
19
64.551
64.550
71.756
71.756
58.947
58.693
20
66.260
66.257
68.719
68.719
55.916
55.638
21
67.936
67.934
65.650
65.652
22
69.577
69.576
62.549
62.552
23
71.185
71.183
59.416
59.417
24
72.758
72.758
56.251
56.252
25
74.297
74.299
53.054
53.056
26
75.802
75.802
49.825
49.822
27
77.273
77.273
46.565
46.564
28
78.710
78.712
43.273
43.272
29
80.112
80.112
39.949
39.947
30
81.481
81.483
36.594
36.591
31
82.815
82.815
33.207
33.206
32
84.115
84.114
29.789
29.791
33
85.380
85.376
26.339
26.339
34
22.858
22.862
ν0=4523.274
B″=1.207728
D″=1.925×10−6
ν0=4510.425
B′−B″=−0.016611
D′−D″=3.580×10−8
B″=1.212096
Table VII
The Ritz combination principle, has been used to obtain the band origins of the 0110–000 bands of isotopic forms of HCN.
HC12N
ν2
(0111–000)–(0111–0110)=713.466
(1111–000)–(1111–0110)=713.457
(0112–000)–(0112–0110)=713.456
(0201–000)–(0201–0110)=713.448
(001–000)–(001–0110)=713.46
HC13N
ν2
(0111–000)–(0111–0110)=707.398
(0112–000)–(0112–0110)=707.400
(0201–000)–(0201–0110)=707.380
DC12N
ν2
(1111–000)–(1111–0110)=570.28
(001–000)–(001–0110)=570.26
(0111–000)–(0111–0110)=570.43
(0112–000)–(0112–0110)=570.48
(0200–000)–(0200–0110)=570.19
Table VIII
Wave numbers of the 0110–000 band of HC12N have been calculated from the measured rotational constants of the 0110 state and the band origin ν0=713.460 cm−1 obtained by applying the Ritz combination principle to near-infrared bands. It is believed that the absolute value of the wave numbers are accurate to ±0.003 cm−1 and the relative values are accurate to ±0.001 cm−1.
J
R(J) cm−1
P(J) cm−1
J
R(J) cm−1
P(J) cm−1
Q(1)
711.989
15
759.192
667.641
0
14.938
16
62.132
64.687
1
17.894
17
65.070
61.734
2
20.849
706.070
18
68.006
58.782
3
23.804
03.112
19
70.940
55.830
4
26.758
00.155
20
73.871
52.878
5
29.712
697.199
21
76.800
49.927
6
32.665
94.242
22
79.727
46.977
7
35.617
91.285
23
82.651
44.027
8
38.568
88.329
24
85.572
41.078
9
41.518
85.372
25
88.491
38.129
10
44.467
82.416
26
91.406
35.181
11
47.415
79.460
27
94.318
32.234
12
50.362
76.505
28
97.226
29.287
13
53.307
73.550
29
800.131
26.341
14
56.250
70.595
30
02.962
23.395
Table IX
The rotational constants and B values for various states of the HC12N molecule. The observed values were obtained from the sources quoted in the fifth column. All constants are in cm−1 units.
See reference 4.
Present measurements.
See reference 2.
See reference 1
See reference 18.
D. H. Rank, T. A. Wiggins, A. H. Guenther, and J. N. Shearer, J. Opt. Soc. Am. 46, 953 (1956).
Table X
Vibrational spectrum of HC12N. Column 3 is the observed position of the band origin for parallel bands, or the Q-branch origin for perpendicular bands. Columns 4 and 5 give the type and magnitude of the correction which must be applied to column 3 to obtain a corrected ν0 observed. The values listed in column 7 were calculated using Eq. (6) and the constants given in Table XI. The last column gives the reference used to obtain the numbers listed in column 3.
See reference 20.
See reference 10.
See reference 3.
See reference 2.
Present measurement.
See reference 1.
Calculated making use of the Ritz Combination Principle and the frequency of the accurately determined band 12°1–000.
See reference 4.
See reference 18.
Perturbation due to Fermi resonance.
Table XI
Vibrational constants of HC12N in wave numbers. The constants with superscript 0 refer to Eq. (6). Those with no superscript refer to Eq. (5).
ω1=2119.8642
y111=−0.1889
ω10=2104.2248
ω2=726.9950
y222=0.0285
ω20=710.8955
ω3=3441.2207
y333=0.27020
ω30=3363.8737
x11=−7.0741
y112=−0.0012
x110=−7.7449
x22=−2.6533
y113=−0.7723
x220=−2.6240
x33=−52.4901
y122=−0.0747
x330=−52.7292
x12=−2.5265
y133=−1.1010
x120=−2.6490
x13=−10.4434
y123=0.1240
x130=−12.1927
x23=−19.0055
y223=−0.0375
x230=−19.1415
y233=−0.1230
y3330=0.30906
g22=5.160
z3333=0.01943
The remaining y0, z0 coefficients are the same as the y, z coefficients.
Table XII
Moments of inertia, B values, and select rotational constants for states of the isotopic forms of HCN used to determine the internuclear distances. All B values are given in wave numbers. The moments of inertia are in g cm2×1039.
HC12N
HC13N
DC12N
B000
1.478219
1.439988
1.207747
B010
1.481828
1.443188
1.212096
α2
0.003609
0.00320
0.00435
B101 − B000
−0.020286
−0.01919
−0.01661
(α1+α3)/2
−0.010143
−0.00959
−0.00831
Be
1.484753
1.44638
1.21170
Ie (meas.)
1.885088
1.93510
2.30988
Ie (calc)
1.885084
1.935103
2.309878
c=2.997930×1010 cm/sec
D=2.0147425
h=6.62517×1027 erg sec
C12=12.0038156
NA=6.02486×1023 molecules/g mol wt
C13=13.0074900
H=1.0081451
N14=14.007526
Tables (12)
Table I
Observed and calculated wave numbers of the lines of the HC12N bands. The calculated wave numbers were obtained by use of the rotational constants quoted. It is believed that the wave numbers listed are relatively accurate to 1 part in 107 and absolutely accurate to 1 part in 3×106.
HC12N
HC12N
HC12N
ν
ν1+ν3
ν2+2ν3−ν2
J
Calc R(J) cm−1
Obs cm−1
Calc P(J) cm−1
Obs cm−1
Calc R(J) cm−1
Obs cm−1
Calc P(J) cm−1
Obs cm−1
Obs R(J) cm−1
Obs P(J) cm−1
0
3314.4089
0.410
5396.614
1
17.3236
3308.5169
99.489
0.486
5390.742
0.744
6486.587
2
20.2173
05.5397
5402.324
0.316
87.745
0.744
89.432
6474.807
3
23.0899
02.5418
05.118
0.122
84.708
92.225
71.772
4
25.9415
3299.5233
07.870
0.874
81.630
68.684
5
28.7718
96.4842
10.582
78.512
65.554
6
31.5810
93.4246
13.253
75.354
6500.316
00.425
7
34.3688
90.3446
0.342
15.883
0.889
72.155
0.156
02.934
59.174
03.067
8
37.1352
87.2443
18.472
0.473
68.917
0.920
05.512
55.973
05.662
55.872
9
39.8802
84.1238
21.020
0.022
65.638
08.052
08.222
10
42.6036
80.9830
0.984
23.526
0.526
62.320
49.362
49.234
11
45.3056
0.302
77.8221
0.824
25.991
0.990
58.962
12.994
45.996
13.205
45.856
12
47.9858
74.6412
28.415
55.564
0.563
15.398
42.581
15.629
42.440
13
50.6444
71.4404
30.797
0.800
52.126
17.770
39.135
18.019
38.978
14
53.2813
68.2196
33.138
0.137
48.649
20.092
35.641
20.363
35.473
15
55.8963
64.9790
35.437
45.132
32.111
31.933
16
58.4894
61.7188
37.694
0.693
41.575
24.612
28.543
24.927
28.353
17
61.0606
58.4388
39.910
0.908
37.979
26.810
24.932
27.148
24.733
18
63.6098
0.610
55.1393
42.084
34.344
0.342
28.960
29.319
19
66.1370
51.8203
44.216
0.216
30.670
0.669
17.581
17.372
20
68.6420
48.4819
46.307
0.301
26.956
13.857
13.635
21
71.1249
45.1242
48.355
0.355
23.203
0.201
35.166
10.076
35.593
09.860
22
73.5856
41.7472
50.361
0.359
19.412
0.411
37.147
06.264
37.599
06.032
23
76.0239
38.3511
0.355
52.325
15.581
0.581
02.415
02.177
24
78.4400
34.9359
54.247
0.249
11.711
0.712
6398.517
98.277
25
80.8336
31.5017
0.501
56.127
07.803
42.839
43.364
26
83.2048
28.0486
57.965
0.970
03.856
0.856
27
85.5535
24.5766
0.575
59.760
0.762
5299.870
28
87.8796
0.877
21.0859
0.090
61.513
95.846
0.847
29
90.1831
0.181
17.5766
0.580
63.223
91.783
30
92.4640
14.0487
64.891
87.682
31
94.7222
10.5023
32
96.9576
06.9375
33
99.1702
0.169
03.3544
B′=1.467799
B′=1.457933
B″=1.481828
B′−B″=−0.010420
B′−B″=−0.020286
B′−B″=−0.020705
ν0=3311.473
ν0=5393.698
D″=3.0773×10−6
Q(0)=6480.785
q′=0.007686
q″=0.007488
Table II
Measured doublet separations in vacuum wave numbers of the l-type doublets. It must be remembered that l-type doublets actually represent two distinct π–π bands. In the R branch the πd component occurs at higher frequency than the πc component. However, in the P branch the order of the components is reversed. Hence the separation is designated with a negative sign.
Band
HC12N
HC12N
HC12N
HC13N
DC12N
m
0111–0110
0112–0110
1111–0110
0112–0110
1111–0110
26
0.523
0.260
25
0.444
0.254
24
0.421
23
0.452
22
0.426
21
20
0.346
19
0.329
0.359
0.344
0.351
0.203
18
0.311
0.338
0.335
0.196
17
0.288
0.315
0.186
16
0.284
0.176
15
0.271
0.267
0.162
14
0.249
0.247
0.244
0.154
13
0.231
0.229
0.224
12
0.211
11
0.189
10
0.163
0.171
0.171
9
0.143
0.150
0.148
8
0.128
0.134
7
0.109
0.108
6
0.099
5
4
0.062
−5
−0.073
−6
−7
−0.098
−0.096
−8
−0.112
−0.101
−0.090
−9
−0.112
−10
−0.128
−0.134
−0.119
−0.117
−11
−0.141
−0.128
−0.144
−12
−0.140
−0.155
−0.141
−13
−0.178
−0.157
−0.168
−0.150
−0.168
−14
−0.188
−0.167
−0.176
−0.163
−0.174
−15
−0.178
−0.189
−0.176
−0.194
−16
−0.209
−0.190
−0.198
−0.177
−0.205
−17
−0.224
−0.200
−0.185
−0.220
−18
−0.195
−0.242
−19
−0.209
−0.199
−0.254
−20
−0.250
−0.222
−0.200
−0.277
−21
−0.216
−22
−0.275
−0.232
−23
−0.238
−24
−0.288
−0.240
−25
−0.300
−26
−0.303
−27
−0.319
−28
−0.325
Table III
Wave numbers of Q branches. Only lines which were well resolved and free from other disturbances are listed. The lines marked ‡ were not used for fitting because they show a deviation from the theoretically predicted values. The numbers marked * are calculated from the quoted constants. The numbers are believed to be accurate to ±0.003 cm−1.
ν2+ν3~π−∑
2ν2+ν3−ν2~∑−π
2ν2+ν3−ν2~Δ−π
ν2+2ν3~π−∑
ν1+ν2+ν3
HC12N
HC13N
HC12N
HC13N
HC12N
HC13N
HC12N
HC13N
HC13N
J
Q(J) cm−1
Q(J) cm−1
Q(J) cm−1
Q(J) cm−1
Q(J) cm−1
Q(J) cm−1
Q(J) cm−1
Q(J) cm−1
Q(J) cm−1
0
*4004.169
*3980.781
*3972.351
*3949.920
*3987.099
*3964.346
*7192.755
*7151.648
*6027.368
1
2
72.271
91.378
3
72.211
91.294
4
91.185
51.410
26.982
5
72.041
49.621
91.055
51.294
26.916
6
04.049
80.673
71.919
49.508
86.666
90.895
26.840
7
04.009
80.634
71.776
49.370
86.496
90.706
50.974
26.748
8
03.963
80.592
71.615
49.207
86.315
63.673
90.494
50.764
26.646
9
03.910
80.543
71.429
49.032
63.470
90.255
26.528
10
03.854
80.490
71.218
48.833
85.920
89.989
50.304
26.401
11
03.790
80.431
70.987
85.692
89.697
50.033
26.259
12
03.721
80.368
70.723
85.452
62.842
89.384
49.735
26.107
13
80.299
‡85.203
62.606
89.025
49.417
25.941
14
80.223
‡70.205
‡84.942
62.346
88.656
49.079
25.761
15
03.479
80.144
‡69.863
‡84.668
88.248
48.713
16
03.385
80.058
‡84.386
87.830
17
03.286
18
03.180
‡68.638
‡83.802
19
‡68.163
‡83.503
20
‡83.198
21
79.548
22
79.427
‡82.584
23
02.565
79.302
24
02.413
79.171
25
02.275
79.035
26
02.120
27
78.743
28
78.588
29
78.425
B′−B″=−0.002859
B′−B″=−0.002633
B′−B″=−0.01034
B′−B″=−0.00987
B′−B″=−0.01059
B′−B″=−0.00957
B′−B″=−0.01334
B′−B″=−0.01228
B′−B″=−0.01257
D′−D″=−8.51×10−8
D′−D″=−8.31×10−8
Table IV
HC13N band origins. The band origins have been corrected for l2B and are given in vacuum wave numbers.
Ritz combination principle.
Present measurements.
See reference 16.
Calculated from 00Z–000 series and the 101–000 band.
Table V
Measured wave numbers and rotational constants of some HC13N bands. Only those lines which are free from blends have been measured. These numbers are believed to be accurate to ±0.003 cm−1.
HC13N
HC13N
HC13N
ν1+ν3
2ν3
ν2+2ν3−ν2
J
Obs R(J) cm−1
Obs P(J) cm−1
Obs R(J) cm−1
Obs P(J) cm−1
Obs R(J) cm−1
Obs P(J) cm−1
0
6486.125
1
5340.775
88.934
6480.406
6451.351
2
77.487
54.121
6439.882
3
34.906
94.418
56.859
36.925
4
5357.478
97.102
71.528
59.549
33.921
5
60.131
28.873
68.493
30.878
6
62.734
25.801
6502.349
64.771
27.800
64.879
7
65.312
22.697
04.914
62.305
24.694
8
67.844
19.547
59.160
69.864
21.540
70.013
9
70.339
09.926
55.968
72.358
72.523
10
72.788
13.142
12.373
15.180
15.061
11
09.883
14.782
49.472
11.917
11.789
12
77.580
06.585
17.144
46.168
79.592
08.625
79.816
08.484
13
79.918
03.246
42.820
81.929
05.287
82.173
05.136
14
82.215
21.761
39.439
84.218
01.912
84.486
01.749
15
84.475
5296.468
24.005
36.020
86.477
6398.505
86.761
98.329
16
86.693
93.015
26.213
32.561
95.052
94.876
17
88.873
89.540
90.867
91.566
91.202
91.381
18
91.012
30.507
25.532
93.004
88.049
93.355
87.854
19
82.452
32.596
84.485
84.286
20
95.174
78.857
34.640
18.355
80.886
80.686
21
97.193
36.646
14.708
22
99.175
38.617
11.024
23
5401.119
40.540
24
42.424
03.545
25
6399.752
26
46.077
27
47.840
B′=1.420802
B′=1.420438
B″=1.44319
B′−B″=−0.019186
B′−B″=−0.019550
B′−B″=−0.019149
ν0=5343.657
ν0=6483.286
D″=2.936×10−6
Q(0)=6445.695
q′=0.00734
q″=0.00713
Table VI
Wave numbers and rotational constants of some DC12N bands.
DC12N
DC12N
ν1+ν3
ν1+ν2+ν3−ν2
J
Calc R(J) cm−1
Obs cm−1
Calc P(J) cm−1
Obs cm−1
Obs R(J) cm−1
Obs P(J) cm−1
0
4525.656
4525.655
1
28.005
28.004
4520.858
4520.856
2
30.321
30.320
18.410
18.409
3
32.603
32.603
15.928
15.928
4519.799
4
34.852
34.852
13.413
13.413
22.061
5
37.067
10.865
10.862
24.280
4497.970
6
39.249
08.284
08.282
26.471
95.388
7
41.397
05.671
05.669
28.636
92.764
8
43.513
43.516
03.025
30.752
90.159
90.069
9
45.594
45.596
00.345
00.344
87.489
87.377
10
47.642
47.644
4497.632
4497.632
84.770
84.653
11
49.656
49.658
94.887
94.890
82.040
81.896
12
51.636
51.637
92.110
92.112
13
53.582
53.582
89.299
89.298
40.820
76.461
40.975
76.293
14
55.495
55.497
86.457
86.457
42.746
73.610
42.908
73.435
15
57.374
57.372
83.581
83.581
44.630
70.746
44.806
70.552
16
59.219
59.219
80.674
80.672
46.486
67.840
46.672
67.635
17
61.030
61.029
77.733
77.735
48.310
64.905
48.506
64.685
18
62.808
62.808
74.761
74.760
50.099
61.943
50.303
61.701
19
64.551
64.550
71.756
71.756
58.947
58.693
20
66.260
66.257
68.719
68.719
55.916
55.638
21
67.936
67.934
65.650
65.652
22
69.577
69.576
62.549
62.552
23
71.185
71.183
59.416
59.417
24
72.758
72.758
56.251
56.252
25
74.297
74.299
53.054
53.056
26
75.802
75.802
49.825
49.822
27
77.273
77.273
46.565
46.564
28
78.710
78.712
43.273
43.272
29
80.112
80.112
39.949
39.947
30
81.481
81.483
36.594
36.591
31
82.815
82.815
33.207
33.206
32
84.115
84.114
29.789
29.791
33
85.380
85.376
26.339
26.339
34
22.858
22.862
ν0=4523.274
B″=1.207728
D″=1.925×10−6
ν0=4510.425
B′−B″=−0.016611
D′−D″=3.580×10−8
B″=1.212096
Table VII
The Ritz combination principle, has been used to obtain the band origins of the 0110–000 bands of isotopic forms of HCN.
HC12N
ν2
(0111–000)–(0111–0110)=713.466
(1111–000)–(1111–0110)=713.457
(0112–000)–(0112–0110)=713.456
(0201–000)–(0201–0110)=713.448
(001–000)–(001–0110)=713.46
HC13N
ν2
(0111–000)–(0111–0110)=707.398
(0112–000)–(0112–0110)=707.400
(0201–000)–(0201–0110)=707.380
DC12N
ν2
(1111–000)–(1111–0110)=570.28
(001–000)–(001–0110)=570.26
(0111–000)–(0111–0110)=570.43
(0112–000)–(0112–0110)=570.48
(0200–000)–(0200–0110)=570.19
Table VIII
Wave numbers of the 0110–000 band of HC12N have been calculated from the measured rotational constants of the 0110 state and the band origin ν0=713.460 cm−1 obtained by applying the Ritz combination principle to near-infrared bands. It is believed that the absolute value of the wave numbers are accurate to ±0.003 cm−1 and the relative values are accurate to ±0.001 cm−1.
J
R(J) cm−1
P(J) cm−1
J
R(J) cm−1
P(J) cm−1
Q(1)
711.989
15
759.192
667.641
0
14.938
16
62.132
64.687
1
17.894
17
65.070
61.734
2
20.849
706.070
18
68.006
58.782
3
23.804
03.112
19
70.940
55.830
4
26.758
00.155
20
73.871
52.878
5
29.712
697.199
21
76.800
49.927
6
32.665
94.242
22
79.727
46.977
7
35.617
91.285
23
82.651
44.027
8
38.568
88.329
24
85.572
41.078
9
41.518
85.372
25
88.491
38.129
10
44.467
82.416
26
91.406
35.181
11
47.415
79.460
27
94.318
32.234
12
50.362
76.505
28
97.226
29.287
13
53.307
73.550
29
800.131
26.341
14
56.250
70.595
30
02.962
23.395
Table IX
The rotational constants and B values for various states of the HC12N molecule. The observed values were obtained from the sources quoted in the fifth column. All constants are in cm−1 units.
See reference 4.
Present measurements.
See reference 2.
See reference 1
See reference 18.
D. H. Rank, T. A. Wiggins, A. H. Guenther, and J. N. Shearer, J. Opt. Soc. Am. 46, 953 (1956).
Table X
Vibrational spectrum of HC12N. Column 3 is the observed position of the band origin for parallel bands, or the Q-branch origin for perpendicular bands. Columns 4 and 5 give the type and magnitude of the correction which must be applied to column 3 to obtain a corrected ν0 observed. The values listed in column 7 were calculated using Eq. (6) and the constants given in Table XI. The last column gives the reference used to obtain the numbers listed in column 3.
See reference 20.
See reference 10.
See reference 3.
See reference 2.
Present measurement.
See reference 1.
Calculated making use of the Ritz Combination Principle and the frequency of the accurately determined band 12°1–000.
See reference 4.
See reference 18.
Perturbation due to Fermi resonance.
Table XI
Vibrational constants of HC12N in wave numbers. The constants with superscript 0 refer to Eq. (6). Those with no superscript refer to Eq. (5).
ω1=2119.8642
y111=−0.1889
ω10=2104.2248
ω2=726.9950
y222=0.0285
ω20=710.8955
ω3=3441.2207
y333=0.27020
ω30=3363.8737
x11=−7.0741
y112=−0.0012
x110=−7.7449
x22=−2.6533
y113=−0.7723
x220=−2.6240
x33=−52.4901
y122=−0.0747
x330=−52.7292
x12=−2.5265
y133=−1.1010
x120=−2.6490
x13=−10.4434
y123=0.1240
x130=−12.1927
x23=−19.0055
y223=−0.0375
x230=−19.1415
y233=−0.1230
y3330=0.30906
g22=5.160
z3333=0.01943
The remaining y0, z0 coefficients are the same as the y, z coefficients.
Table XII
Moments of inertia, B values, and select rotational constants for states of the isotopic forms of HCN used to determine the internuclear distances. All B values are given in wave numbers. The moments of inertia are in g cm2×1039.