Microwave Spectrum, and Conformational
Composition of Chloromethylphosphine (ClCH2PH2)
Harald Møllendal,*,ϯ Alexey Konovalov,ϯ and Jean-Claude Guillemin‡,§
Centre for Theoretical and Computational Chemistry (CTCC), Department of Chemistry,
University of Oslo, P. O. Box 1033 Blindern, NO-0315 Oslo, Norway, École Nationale
Supérieure de Chimie de Rennes, CNRS, UMR 6226, Avenue du Général Leclerc, CS 50837,
35708 Rennes Cedex 7, France and Université européenne de Bretagne.
Supporting Information
*To whom correspondence should be addressed. Tel: +47 2285 5674; Fax: +47 2285 5441; Email: harald.mollendal@kjemi.uio.no
ϯUniversity
‡École
§
of Oslo
Nationale Supérieure de Chimie de Rennes
Université européenne de Bretagne
1
TABLE 1S: MP2/aug-cc-pVQZ Vibrational Frequencies of Conformer I of ClCH2PH2.
Frequencies -Red. masses -Frc consts -IR Inten
-Atom AN
X
1
6
0.00
2
1
0.02
3
1
-0.02
4 15
0.00
5
1
0.32
6
1
-0.32
7 17
0.00
1
A"
231.9959
1.1544
0.0366
5.8256
Y
Z
0.00
0.08
-0.10
0.16
0.10
0.16
0.00 -0.04
0.41
0.43
-0.41
0.43
0.00 -0.03
X
0.00
0.04
0.04
0.25
0.58
0.58
-0.26
2
A'
251.6109
6.1349
0.2288
5.6166
Y
Z
-0.26
0.00
-0.24 -0.02
-0.24
0.02
0.05
0.00
-0.08
0.01
-0.08 -0.01
0.07
0.00
X
-0.02
-0.20
-0.20
0.17
-0.49
-0.49
-0.10
3
A'
628.0925
4.2354
0.9845
15.1673
Y
Z
0.38
0.00
0.32
0.03
0.32 -0.03
-0.09
0.00
0.13 -0.04
0.13
0.04
-0.07
0.00
Frequencies -Red. masses -Frc consts -IR Inten
-Atom AN
X
1
6
0.00
2
1
-0.17
3
1
0.17
4 15
0.00
5
1
0.42
6
1
-0.42
7 17
0.00
4
A"
643.0770
1.1001
0.2681
0.6045
Y
Z
0.00
0.09
0.43 -0.23
-0.43 -0.23
0.00
0.00
-0.22 -0.03
0.22 -0.03
0.00 -0.01
X
0.56
0.54
0.54
-0.11
-0.03
-0.03
-0.13
5
A'
798.3659
5.8040
2.1796
21.2257
Y
Z
0.06
0.00
0.03
0.02
0.03 -0.02
0.07
0.00
0.14
0.07
0.14 -0.07
-0.09
0.00
X
-0.03
0.05
0.05
-0.03
0.65
0.65
0.00
6
A'
862.8045
1.3071
0.5733
10.9834
Y
Z
0.14
0.00
0.12
0.02
0.12 -0.02
-0.03
0.00
-0.20
0.08
-0.20 -0.08
-0.01
0.00
Frequencies -Red. masses -Frc consts -IR Inten
-Atom AN
X
1
6
0.00
2
1
0.12
3
1
-0.12
4 15
0.00
5
1
-0.49
6
1
0.49
7 17
0.00
7
A"
966.5957
1.2810
0.7052
16.5795
Y
Z
0.00
0.15
0.39 -0.13
-0.39 -0.13
0.00 -0.03
0.26
0.02
-0.26
0.02
0.00 -0.01
8
A'
1129.2945
1.0405
0.7818
14.7592
X
Y
Z
0.00
0.01
0.00
0.11
0.02
0.00
0.11
0.02
0.00
0.00
0.03
0.00
-0.11 -0.50 -0.47
-0.11 -0.50
0.47
0.00
0.00
0.00
9
A"
1194.6395
1.0233
0.8605
1.4940
X
Y
Z
0.00
0.00
0.00
0.68
0.06 -0.02
-0.68 -0.06 -0.02
0.00
0.00
0.02
0.15 -0.10 -0.02
-0.15
0.10 -0.02
0.00
0.00 -0.01
10
A'
Frequencies -- 1254.6003
Red. masses -1.1835
Frc consts -1.0975
IR Inten
-9.5275
Atom AN
X
Y
Z
1
6
-0.12
0.01
0.00
2
1
0.69
0.01
0.02
3
1
0.69
0.01 -0.02
4 15
0.01
0.00
0.00
5
1
-0.07
0.10
0.07
6
1
-0.07
0.10 -0.07
7 17
0.00 -0.01
0.00
11
A'
1458.2916
1.0743
1.3460
4.2059
X
Y
Z
0.00
0.08
0.00
-0.01 -0.56
0.43
-0.01 -0.56 -0.43
0.00
0.00
0.00
0.00 -0.01 -0.01
0.00 -0.01
0.01
0.00
0.00
0.00
12
A'
2477.2042
1.0345
3.7402
22.2044
X
Y
Z
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.01
0.00
0.01
0.03
0.00
-0.17 -0.43
0.53
-0.17 -0.43 -0.53
0.00
0.00
0.00
2
13
A"
Frequencies -- 2487.3529
Red. masses -1.0417
Frc consts -3.7971
IR Inten
-35.9895
Atom AN
X
Y
Z
1
6
0.00
0.00
0.00
2
1
0.00
0.01
0.01
3
1
0.00 -0.01
0.01
4 15
0.00
0.00
0.03
5
1
0.19
0.44 -0.52
6
1
-0.19 -0.44 -0.52
7 17
0.00
0.00
0.00
14
A'
3116.2686
1.0573
6.0495
5.7442
X
Y
Z
0.00 -0.07
0.00
-0.02
0.39
0.58
-0.02
0.39 -0.58
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.01
0.00
0.00
0.00
0.00
15
A"
3184.6102
1.1082
6.6217
0.0590
X
Y
Z
0.00
0.00 -0.10
-0.02
0.41
0.57
0.02 -0.41
0.57
0.00
0.00
0.00
0.00 -0.01
0.01
0.00
0.01
0.01
0.00
0.00
0.00
3
TABLE 2S: MP2/aug-cc-pVTZ Vibrational Frequencies of Conformer II of ClCH2PH2.
Frequencies -Red. masses -Frc consts -IR Inten
-Atom AN
X
1
6
0.01
2
1
0.00
3
1
0.04
4 15
0.03
5
1
0.01
6
1
0.50
7 17
-0.04
1
A
170.2898
1.2258
0.0209
2.9841
Y
Z
-0.05
0.07
-0.11
0.11
0.01
0.12
-0.01
0.01
0.18 -0.65
0.46
0.18
0.01 -0.03
Frequencies -Red. masses -Frc consts -IR Inten
-Atom AN
X
1
6
0.08
2
1
-0.13
3
1
0.24
4 15
-0.03
5
1
0.18
6
1
0.44
7 17
-0.03
4
A
696.5967
1.2304
0.3518
1.2998
Y
Z
0.02
0.07
0.45 -0.20
-0.38 -0.26
0.03
0.01
-0.14 -0.08
-0.42 -0.15
-0.02 -0.01
Frequencies
Red. masses
Frc consts
IR Inten
7
A
944.7061
1.2955
0.6812
19.2973
Atom AN
1
6
2
1
3
1
4 15
5
1
6
1
7 17
-----
X
0.02
0.03
-0.13
0.01
0.03
-0.55
0.00
Y
-0.04
0.38
-0.43
0.00
-0.04
0.51
0.00
X
-0.01
0.03
0.01
0.27
-0.14
-0.02
-0.23
2
A
230.2161
5.8070
0.1813
1.1691
Y
Z
-0.22 -0.08
-0.15 -0.13
-0.26 -0.12
0.05 -0.01
0.22
0.65
-0.41 -0.17
0.05
0.03
X
0.44
0.49
0.30
-0.08
-0.06
-0.38
-0.09
5
A
737.4353
3.9604
1.2689
15.3812
Y
Z
-0.03 -0.07
-0.36
0.13
0.22
0.14
0.07
0.01
0.05
0.03
0.27
0.07
-0.06
0.01
8
A
1102.6850
1.0342
0.7409
17.8157
Z
0.14
-0.12
-0.15
-0.04
0.10
0.15
-0.01
X
0.00
-0.15
0.10
0.02
-0.09
-0.56
0.00
Y
0.00
0.02
0.00
0.00
0.25
-0.40
0.00
X
0.02
-0.09
-0.20
0.10
0.58
-0.17
-0.10
3
A
606.4222
3.2842
0.7116
16.9513
Y
Z
0.35
0.01
0.18
0.11
0.39
0.07
-0.06 -0.01
-0.45 -0.10
0.14
0.06
-0.08
0.00
X
-0.03
-0.06
-0.10
-0.01
0.74
-0.15
0.01
6
A
865.3995
1.2936
0.5708
19.4447
Y
Z
-0.12 -0.03
-0.20
0.01
-0.02
0.05
0.05
0.01
-0.56 -0.21
-0.01 -0.02
0.02
0.00
9
A
1142.2687
1.0304
0.7921
6.4098
Z
0.01
0.00
0.00
0.02
-0.63
-0.14
0.00
X
-0.01
0.74
-0.60
0.00
0.00
0.07
0.00
Y
0.01
0.09
-0.10
0.00
0.04
-0.22
0.00
Z
0.01
0.00
-0.03
0.02
-0.14
-0.06
-0.01
4
10
A
Frequencies -- 1230.5602
Red. masses -1.1602
Frc consts -1.0351
IR Inten
-20.1568
Atom AN
X
Y
Z
1
6
-0.11
0.01
0.01
2
1
0.62
0.06
0.01
3
1
0.76
0.03 -0.04
4 15
0.00
0.01
0.00
5
1
0.09 -0.06 -0.02
6
1
-0.09
0.05
0.01
7 17
-0.01 -0.01
0.00
11
A
1455.4121
1.0783
1.3457
1.6409
X
Y
Z
0.01 -0.08 -0.01
0.01
0.59 -0.39
-0.02
0.54
0.45
0.00
0.00
0.00
0.00 -0.01
0.01
0.01
0.00
0.00
0.00
0.00
0.00
12
A
2357.1195
1.0371
3.3949
67.5416
X
Y
Z
0.00
0.00
0.00
0.00
0.00 -0.01
0.00
0.00
0.00
-0.02 -0.02 -0.01
0.65
0.73
0.17
0.00 -0.06
0.12
0.00
0.00
0.00
13
A
Frequencies -- 2387.6527
Red. masses -1.0395
Frc consts -3.4915
IR Inten
-50.1858
Atom AN
X
Y
Z
1
6
0.00
0.00
0.00
2
1
0.00
0.00
0.00
3
1
0.00 -0.01
0.01
4 15
0.00 -0.01
0.03
5
1
0.08
0.10
0.04
6
1
0.01
0.33 -0.93
7 17
0.00
0.00
0.00
14
A
3090.3473
1.0557
5.9401
7.7742
X
Y
Z
0.01 -0.07
0.01
-0.02
0.30
0.53
-0.04
0.47 -0.63
0.00
0.00
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
15
A
3153.1405
1.1114
6.5104
0.2453
X
Y
Z
0.00
0.00 -0.10
-0.04
0.41
0.67
0.04 -0.38
0.47
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.00
5
TABLE 3S: B3LYP/aug-cc-pVTZ Harmonic and Anharmonic Vibrational Fundamentals of
Conformer I of ClCH2PH2
Harmonic(cm-1)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
3085.865
2394.140
1443.621
1246.563
1112.393
854.169
725.047
590.246
243.203
3141.814
2403.143
1173.911
950.441
638.155
219.464
Anharmonic(cm-1)
2980.069
2314.419
1423.522
1220.432
1099.706
840.679
704.857
579.024
242.133
2995.109
2323.166
1150.180
938.198
645.807
239.771
6
TABLE 4S: B3LYP/aug-cc-pVTZ Vibration-Rotation -Matrixa of Conformer I of
ClCH2PH2
Q( 1)
Q( 2)
Q( 3)
Q( 4)
Q( 5)
Q( 6)
Q( 7)
Q( 8)
Q( 9)
Q(10)
Q(11)
Q(12)
Q(13)
Q(14)
Q(15)
a
a
21.92971
59.64288
48.45835
110.83956
71.28146
-48.50237
230.05406
-59.53646
-288.50693
-17.20634
38.40760
169.35562
-31.15356
-106.75005
209.59229
b
-0.08953
0.57281
0.79089
-1.99378
-2.45265
6.31033
10.74689
14.49925
0.04062
-0.42441
0.17596
-3.17867
6.92665
8.47702
2.69728
c
-0.52709
0.24164
-1.62402
3.41701
-2.89402
6.44930
10.11268
15.47457
3.30217
-0.71561
0.22902
-3.16128
5.91642
6.47980
1.48968
In MHz.
7
TABLE 5S: B3LYP/aug-cc-pVTZ Harmonic and Anharmonic Vibrational Fundamentals of
Conformer II of ClCH2PH2
Harmonic(cm-1)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
3153.141
3090.347
2387.653
2357.119
1455.412
1230.560
1142.269
1102.685
944.706
865.400
737.435
696.597
606.422
230.216
170.290
Anharmonic(cm-1)
3000.525
2981.822
2277.577
2272.072
1434.091
1207.364
1121.160
1066.868
925.367
866.233
717.710
685.652
600.963
229.381
136.755
8
TABLE 6S: B3LYP/aug-cc-pVTZ Vibration-Rotation -Matrixa of Conformer II of
ClCH2PH2
Q( 1)
Q( 2)
Q( 3)
Q( 4)
Q( 5)
Q( 6)
Q( 7)
Q( 8)
Q( 9)
Q(10)
Q(11)
Q(12)
Q(13)
Q(14)
Q(15)
a
a
-9.28047
20.19420
50.45989
90.14022
48.90957
118.42933
177.61728
-17.47788
-58.30067
50.95943
210.73447
-23.47165
-81.62232
-154.64635
57.28722
b
-0.22334
0.26775
1.16851
-3.56185
1.47363
-4.19356
-6.06695
-2.08077
4.70676
6.88786
6.74649
8.86615
16.63153
-0.82623
4.69913
c
-0.46006
-0.20861
0.27624
-1.93170
-0.99912
1.82435
-5.82775
-2.55585
6.76819
4.53233
7.74520
7.60183
16.76689
2.14437
3.39400
In MHz
9
Comments for the Spectroscopic Tables:
Hamiltonian: Watson’s A-reduction Ir representation1
Transition labels: J’’ K-1’’ K+1’’ J’ K-1’ J K+1’
obs. – calc.: the observed – the calculated residuals
weight: the estimated uncertainties of the observed frequencies. Each transition is weighted according to
the inverse square of its estimated uncertainty
t: Student’s t-test2
distortion correction: centrifugal distortion correction
total: correction from quartic and sextic (if included) centrifugal distortion constants
higher: contribution from sextic centrifugal distortion constants
fixed: contribution from fixed quartic and/or fixed sextic centrifugal distortion constants. The values of
fixed constants are also displayed
rms deviation: root-mean-square deviation. Defined dimensionless in a weighted least-squares fit2
: Ray’s asymmetry parameter defined by  = (2B – A – C)/(A – C)
Pseudo-inertial defect: defined by  = Ic – Ia – Ib
Uncertainties: The uncertainties represent one standard deviation
Significant digits: the number of significant digits of each fitted constant is listed on the diagonal of the
correlation matrix
Units: the observed frequencies, the residuals, the distortion corrections, and the rotational constants are
in MHz, the quartic centrifugal distortion constants are in kHz, the sextic centrifugal distortion constants
(if applied) are in Hz, and the principal axis inertial constants and the inertial defect are in u Å2
The spectra have been corrected for nuclear quadrupole interactions using aa = −37.94 andbb =
3.14 MHz for 35Cl species, and aa = −30.17 andbb = 2.75 MHz for the 37Cl isotopologue of
conformer I, while aa = −34.31 andbb = −1.94 MHz were used for the 35Cl variant, and aa =
−27.04 andbb = −1.53 for the 37Cl species of ClCH2PH2 (see article).
The spectra corrected for quadrupole interaction were fitted using Rotfit.3
10
TABLE 7S:
35
ClCH2PH2
Microwave
Spectrum
of
the
Ground
Vibrational
State
of
Conformer
I
of
Watson S-reduction
Total number of transitions: 288
Transition
3
4
4
4
4
5
5
5
5
5
5
6
6
6
6
6
6
6
7
7
7
7
7
7
7
7
7
8
8
8
8
8
8
8
8
8
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
1
0
0
1
1
0
1
0
0
1
1
0
1
0
0
1
2
2
0
1
1
0
1
2
2
3
3
0
1
1
0
1
1
2
2
3
0
1
1
1
1
2
2
3
3
3
3
4
4
5
5
2
4
4
4
3
5
4
5
5
5
4
6
6
6
6
6
5
4
7
7
6
7
6
6
5
5
4
8
8
7
8
8
7
7
6
5
9
9
8
9
8
8
7
7
7
6
6
6
5
5
4
4
5
5
5
5
5
5
6
6
6
6
6
6
7
7
7
7
7
7
7
7
8
8
8
8
8
8
8
8
8
9
9
9
9
9
9
9
9
9
10
10
10
10
10
10
10
10
10
10
10
10
1 3
1 5
0 5
1 5
1 4
1 4
2 3
1 6
0 6
1 6
1 5
1 5
2 5
1 7
0 7
1 7
2 6
2 5
1 6
2 6
2 5
1 8
1 7
2 7
2 6
3 6
3 5
1 7
2 7
2 6
1 9
0 9
1 8
2 8
2 7
3 6
1 8
2 8
2 7
0 10
1 9
2 9
2 8
3 8
3 8
3 7
3 7
4 7
4 6
5 6
5 5
obs. frequency
24340.870
50964.900
29855.530
29337.250
30422.660
24365.210
66511.340
56309.840
35809.420
35200.220
36502.440
25058.270
70369.550
61561.980
41753.570
41060.840
41829.210
41916.230
25884.550
71138.210
65257.880
66727.580
48653.380
47798.930
47929.320
47837.260
47839.420
26850.920
72018.610
64533.710
71814.410
34567.170
54723.580
53766.600
53951.880
53824.020
27966.080
73011.130
63762.120
41309.030
60789.570
59731.320
59985.120
59804.890
59804.890
59810.510
59810.710
59794.800
59794.800
59791.900
59791.900
obs.- weight
calc.
0.191
-0.166
-0.025
-0.242
0.053
-0.087
0.099
-0.170
0.176
-0.279
0.102
-0.121
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0.130
0.192
0.108
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0.151
0.282
0.570
0.003
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0.060
0.089
0.032
0.310
0.046
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0.151
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0.038
0.238
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0.15
0.25
0.10
0.10
0.15
0.25
0.25
0.25
0.15
0.10
0.10
0.25
0.25
0.25
0.10
0.10
0.10
0.10
0.25
0.25
0.25
0.25
0.15
0.10
0.10
0.15
0.10
0.25
0.25
0.25
0.25
0.25
0.20
0.10
0.10
0.15
0.25
0.25
0.25
0.25
0.15
0.10
0.10
0.10
0.10
0.20
0.10
0.15
0.15
0.15
0.15
t
0.9
-0.5
-0.2
-1.8
0.3
-0.3
0.3
-0.5
0.8
-2.0
0.7
-0.3
-0.2
0.3
0.4
-2.1
-1.3
-0.4
0.8
1.0
0.4
0.6
0.5
-1.8
0.7
-1.2
1.1
0.8
1.6
0.0
0.2
-1.1
0.5
-0.3
0.4
0.4
0.1
0.9
0.1
-1.1
0.9
-1.2
1.1
-0.5
-0.5
0.1
1.7
-1.9
-2.1
-1.1
-1.1
distortion corrections
total
higher
fixed
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-0.409
-0.572
0.159
-1.992
-0.354
-1.159
-0.805
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0.598
0.598
4.007
4.007
9.1E-5
3.1E-4
1.4E-4
2.4E-4
2.4E-4
1.7E-4
9.2E-4
7.1E-4
3.5E-4
5.4E-4
5.4E-4
3.6E-4
1.1E-3
1.4E-3
7.6E-4
1.1E-3
1.6E-3
1.6E-3
6.6E-4
1.6E-3
1.6E-3
2.6E-3
1.9E-3
2.9E-3
2.9E-3
2.9E-3
2.9E-3
1.1E-3
2.6E-3
2.6E-3
4.4E-3
1.5E-3
3.3E-3
4.8E-3
4.8E-3
5.6E-3
1.8E-3
4.1E-3
4.1E-3
2.7E-3
5.4E-3
7.7E-3
7.6E-3
9.5E-3
9.5E-3
9.5E-3
9.5E-3
8.0E-3
8.0E-3
-9.1E-4
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11
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
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
13
13
13
13
13
14
14
14
14
15
15
0
1
1
1
1
2
2
3
3
4
4
5
5
6
6
0
1
1
0
1
1
1
2
2
3
4
4
9
9
10
10
11
11
0
0
1
1
2
2
3
3
6
6
8
8
10
10
11
11
12
12
0
1
1
1
2
3
0
1
2
0
1
10
9
10
9
9
9
8
8
7
7
6
6
5
5
4
11
11
10
11
11
11
10
10
9
9
8
7
3
2
2
1
1
0
12
12
12
12
11
10
10
9
7
6
5
4
3
2
2
1
1
0
13
13
12
13
12
12
14
13
13
15
14
10
10
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
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
14
14
13
14
14
15
15
15
1
2
0
1
1
2
2
3
3
4
4
5
5
6
6
1
2
2
0
0
1
1
2
2
3
4
4
9
9
10
10
11
11
1
0
0
1
2
2
3
3
6
6
8
8
10
10
11
11
12
12
1
2
2
0
1
4
1
2
1
1
2
9
8
11
10
10
10
9
9
8
8
7
7
6
6
5
10
10
9
12
12
12
11
11
10
10
9
8
4
3
3
2
2
1
11
13
13
13
12
11
11
10
8
7
6
5
4
3
3
2
2
1
12
12
11
14
13
9
13
12
14
14
13
29239.920
62957.640
48092.540
66850.470
66850.670
65693.480
66029.620
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65772.450
30681.570
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32301.170
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0.5
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0.8
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12
15
16
16
16
17
17
17
18
18
18
18
18
19
19
19
19
19
20
20
20
20
21
21
21
21
21
21
22
22
22
22
23
24
24
24
24
24
25
25
25
25
26
26
26
26
27
27
27
27
27
28
29
29
29
30
30
30
30
30
31
31
32
2
0
1
2
3
3
0
3
3
0
1
2
3
3
0
1
2
3
3
0
1
3
3
4
4
1
3
3
0
1
3
1
4
4
1
3
3
4
4
1
3
4
4
1
3
4
4
1
3
3
1
5
5
1
5
5
1
4
4
1
4
5
14
16
15
15
15
14
17
16
15
18
17
17
17
16
19
18
18
18
17
20
19
19
18
18
17
20
19
19
22
21
20
22
21
20
23
22
21
22
21
24
22
23
22
25
23
24
23
26
25
24
27
25
24
28
26
25
29
27
26
30
27
28
16
16
16
17
16
16
17
17
17
18
18
19
18
18
19
19
20
19
19
20
20
20
20
20
20
21
22
21
22
22
23
23
23
23
24
25
25
24
24
25
26
25
25
26
27
26
26
27
28
28
28
28
28
29
29
29
30
31
31
31
32
31
1
1
2
1
4
4
1
4
4
1
2
1
4
4
1
2
1
4
4
1
2
4
4
5
5
2
2
4
1
2
2
2
5
5
2
2
2
5
5
2
2
5
5
2
2
5
5
2
2
2
2
6
6
2
6
6
2
3
3
2
3
6
15
15
14
16
12
13
16
13
14
17
16
18
14
15
18
17
19
15
16
19
18
16
17
15
16
19
20
18
21
20
21
21
18
19
22
23
24
19
20
23
25
20
21
24
26
21
22
25
26
27
26
22
23
27
23
24
28
28
29
29
30
25
41593.130
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0.225
0.269
-0.192
-0.189
0.247
0.166
0.340
0.268
-0.282
-0.281
0.287
-0.338
-0.337
0.304
0.226
0.376
0.317
0.454
-0.459
13
32
32
32
32
32
32
33
33
33
33
33
34
34
34
35
35
35
36
37
38
38
39
39
39
40
40
40
40
41
41
41
41
42
42
42
43
43
44
44
45
45
45
46
46
47
47
47
47
48
48
48
49
49
49
49
50
50
50
51
51
53
53
5
5
5
1
4
4
5
5
5
5
1
5
5
1
5
5
4
5
5
5
5
6
5
5
6
6
5
5
6
6
5
5
6
6
5
5
5
5
5
5
6
6
6
6
7
7
6
6
7
7
6
7
7
6
6
7
7
6
6
6
6
7
28
27
27
31
29
28
29
29
28
28
32
30
29
33
31
30
32
31
33
34
33
33
35
34
35
34
36
35
36
35
37
36
37
36
37
39
38
40
39
40
40
39
41
40
41
40
42
41
42
41
43
43
42
44
43
44
43
44
46
45
47
47
31
31
31
32
33
33
32
32
32
32
33
33
33
34
34
34
36
35
38
39
39
38
40
40
39
39
41
41
40
40
42
42
41
41
43
44
44
45
45
46
46
46
47
47
46
46
48
48
47
47
49
48
48
50
50
49
49
51
52
52
54
54
6
6
6
2
3
3
6
6
6
6
2
6
6
2
6
6
3
6
4
4
4
7
4
4
7
7
4
4
7
7
4
4
7
7
4
4
4
4
4
4
5
5
5
5
8
8
5
5
8
8
5
8
8
5
5
8
8
5
5
5
5
6
25
26
26
30
30
31
26
26
27
27
31
27
28
32
28
29
33
30
34
35
36
32
36
37
32
33
37
38
33
34
38
39
34
35
40
40
41
41
42
43
41
42
42
43
38
39
43
44
39
40
44
40
41
45
46
41
42
47
47
48
50
48
57346.420
57316.820
57316.620
70981.330
49726.170
37482.410
51256.980
51257.100
51216.860
51216.780
73724.590
45157.300
45103.480
76729.620
39047.200
38975.560
73140.960
32831.310
28238.100
34961.000
31469.520
60692.580
41776.460
37549.430
54613.200
54602.850
48694.540
43605.870
48517.040
48503.310
55724.270
49633.520
42411.340
42393.010
55625.380
70156.690
61573.990
77580.050
67471.730
73309.430
29916.300
28890.150
36384.100
35122.890
58056.240
58053.100
42902.540
41359.920
51971.180
51967.240
49477.250
45877.940
45873.320
56113.760
53840.930
39776.430
39770.300
60078.940
69599.530
66311.520
78744.340
32088.670
-0.021
0.126
-0.074
-0.054
-0.416
-0.031
-0.035
0.085
0.118
0.038
-0.134
-0.113
0.083
-0.276
-0.053
0.119
0.210
-0.215
0.041
-0.079
-0.017
-0.045
-0.404
0.012
-0.011
-0.094
-0.117
-0.166
0.017
0.030
0.223
0.044
0.102
0.032
0.221
-0.189
0.178
0.161
0.294
0.145
-0.113
-0.111
0.133
0.040
0.354
-0.264
0.185
-0.319
0.292
-0.278
0.294
0.137
-0.009
0.091
0.001
0.166
-0.059
-0.102
-0.229
0.005
0.011
0.255
0.10
0.10
0.10
0.25
0.15
0.10
0.10
0.10
0.10
0.10
0.25
0.10
0.10
0.25
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.15
0.10
0.10
0.10
0.10
0.15
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
-0.2
0.9
-0.5
-0.2
-2.1
-0.2
-0.3
0.6
0.9
0.3
-0.4
-0.8
0.6
-1.0
-0.4
0.9
1.8
-1.6
0.3
-0.6
-0.1
-0.3
-2.0
0.1
-0.1
-0.7
-0.9
-0.8
0.1
0.2
1.7
0.3
0.8
0.2
1.7
-1.6
1.4
1.7
2.4
1.3
-0.9
-0.8
1.0
0.3
2.6
-2.0
1.4
-2.4
2.2
-2.1
2.2
1.0
-0.1
0.7
0.0
1.3
-0.4
-0.8
-2.0
0.0
0.1
1.9
192.581
193.181
193.181
-115.555
-389.770
-253.615
223.897
223.897
224.757
224.757
-144.853
256.944
258.164
-177.947
291.775
293.488
-549.336
330.822
-500.243
-553.370
-475.828
370.377
-611.143
-513.090
416.137
416.524
-674.028
-550.982
464.306
464.849
-742.517
-589.258
514.674
515.430
-627.623
-898.365
-665.730
-986.756
-703.173
-739.482
-845.344
-804.624
-915.507
-863.471
692.890
693.043
-990.312
-924.223
758.900
759.114
-1070.209
827.502
827.798
-1155.700
-1050.978
898.765
899.170
-1116.661
-1345.771
-1183.598
-1320.096
-1336.358
-0.459
-0.457
-0.457
0.326
0.284
0.549
-0.525
-0.525
-0.523
-0.523
0.330
-0.595
-0.593
0.328
-0.672
-0.668
0.397
-0.749
0.742
0.820
1.052
-1.211
0.903
1.213
-1.348
-1.347
0.990
1.398
-1.493
-1.491
1.079
1.614
-1.648
-1.645
1.863
1.259
2.152
1.348
2.486
2.873
2.077
2.253
2.278
2.513
-2.975
-2.974
2.493
2.806
-3.243
-3.242
2.720
-3.527
-3.526
2.960
3.502
-3.829
-3.827
3.915
3.468
4.380
5.489
4.779
14
53
54
56
56
57
57
58
59
59
59
60
60
61
61
62
62
63
63
64
65
65
66
66
67
67
67
69
69
70
71
71
73
73
74
74
75
75
75
75
76
76
77
77
79
79
81
81
85
85
86
86
7
7
7
7
7
7
7
9
9
7
9
9
9
9
9
9
8
8
8
8
8
8
8
10
10
8
10
10
9
10
10
10
10
10
10
10
10
11
11
11
11
11
11
11
11
11
11
12
12
12
12
46
48
50
49
51
50
51
51
50
52
52
51
53
52
54
53
56
55
56
58
57
59
58
58
57
60
60
59
61
62
61
64
63
65
64
66
65
65
64
66
65
67
66
69
68
71
70
74
73
75
74
54
55
57
57
58
58
59
58
58
60
59
59
60
60
61
61
64
64
65
66
66
67
67
66
66
68
68
68
71
70
70
72
72
73
73
74
74
74
74
75
75
76
76
78
78
80
80
84
84
85
85
6
6
6
6
6
6
6
10
10
6
10
10
10
10
10
10
7
7
7
7
7
7
7
11
11
7
11
11
8
11
11
11
11
11
11
11
11
12
12
12
12
12
12
12
12
12
12
13
13
13
13
rms deviation:
49
49
51
52
52
53
54
48
49
55
49
50
50
51
51
52
57
58
59
59
60
60
61
55
56
61
57
58
64
59
60
61
62
62
63
63
64
62
63
63
64
64
65
66
67
68
69
71
72
72
73
31743.700
38429.820
51204.460
50561.790
57642.180
56857.800
63164.300
77327.950
77327.950
69480.440
71288.530
71288.530
65244.060
65244.060
59194.460
59194.460
46910.600
46741.390
53012.600
59553.510
59297.660
65909.240
65595.910
75041.950
75041.950
72289.320
62992.700
62992.700
42692.000
50926.460
50926.460
38842.000
38842.000
32792.400
32792.400
26737.730
26737.730
72935.680
72935.680
66935.220
66935.220
60931.300
60931.300
48913.290
48913.290
36880.710
36880.710
59086.240
59086.240
53106.820
53106.820
-0.046
-0.406
0.282
-0.065
0.394
-0.117
-0.200
-0.121
-0.043
-0.174
-0.018
0.086
-0.047
0.093
-0.075
0.111
-0.178
0.086
-0.175
-0.138
-0.042
0.269
-0.209
-0.078
-0.054
0.253
-0.021
0.021
-0.258
-0.082
-0.009
-0.114
0.013
-0.210
-0.045
-0.270
-0.057
-0.002
0.005
0.184
0.193
0.124
0.136
0.001
0.023
-0.229
-0.192
0.425
0.428
-0.150
-0.145
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.15
0.15
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.15
0.15
0.20
0.20
0.20
0.25
0.25
0.25
0.25
0.20
0.20
0.15
0.15
0.20
0.20
0.25
0.25
0.20
0.20
0.20
0.20
0.25
0.25
0.20
0.20
-0.3
-3.1
2.1
-0.5
3.0
-0.9
-1.5
-1.0
-0.3
-1.4
-0.1
0.7
-0.4
0.7
-0.4
0.5
-1.4
0.7
-1.4
-1.1
-0.3
2.3
-1.8
-0.7
-0.5
2.4
-0.1
0.1
-1.0
-0.3
-0.0
-0.3
0.0
-0.6
-0.1
-1.1
-0.2
-0.0
0.0
0.7
0.7
0.4
0.4
0.0
0.1
-0.9
-0.8
1.4
1.4
-0.7
-0.6
-1313.441
-1427.165
-1622.577
-1575.377
-1727.895
-1668.431
-1764.281
1349.972
1349.982
-1862.840
1453.337
1453.350
1559.910
1559.928
1669.757
1669.783
-2236.204
-2217.613
-2337.759
-2491.452
-2461.709
-2626.886
-2589.498
2047.444
2047.448
-2767.958
2315.420
2315.428
-2998.055
2598.233
2598.248
2896.452
2896.479
3051.524
3051.560
3210.673
3210.721
2942.639
2942.641
3107.063
3107.065
3275.555
3275.558
3625.022
3625.028
3991.611
3991.621
4463.331
4463.333
4672.454
4672.456
4.919
5.194
6.114
6.437
6.620
7.043
7.706
-9.366
-9.366
8.433
-10.034
-10.034
-10.732
-10.732
-11.465
-11.465
11.204
11.366
12.266
12.960
13.237
13.923
14.282
-17.269
-17.269
14.944
-19.461
-19.461
19.133
-21.862
-21.861
-24.503
-24.503
-25.926
-25.925
-27.422
-27.421
-29.759
-29.759
-31.404
-31.404
-33.119
-33.119
-36.783
-36.783
-40.791
-40.790
-53.568
-53.568
-56.204
-56.204
1.3717
Rotational constants (MHz) and kappa:
25682.2560
3097.27788
2880.19291 -0.98095918
+0.0093
0.0013
0.0013
0.00000008
15
Inertial constants and defect (uÅ**2):
19.6781418
163.168787
+0.0000072
0.000068
175.467092
0.000082
-7.379837
0.000050
Quartic distortion constants:
1.361729
-18.93903
+0.0016
0.030
255.388
0.21
-0.1625455
0.00037
-0.0034711
0.00015
Sextic distortion constants:
0.00743565
0.247282
+- 0.00066
0.028
-2.4111
0.29
21.208
3.7
0
fixed
0
fixed
0
fixed
Significant Digits and Correlation Matrix:
9
0.510
0.694
0.513
0.940
7
0.848
9
0.844
0.780
9
0.611
0.698
0.648
7
-0.015
-0.389
-0.084
-0.484
-0.735
6
0.282
-0.044
0.415
0.360
0.066
0.462
7
-0.374
-0.167
-0.369
-0.591
-0.358
-0.198
-0.868
5
-0.172
-0.102
-0.068
-0.376
-0.324
0.088
-0.392
0.685
6
-0.211
-0.191
-0.107
-0.463
-0.424
0.181
-0.339
0.669
0.989
6
0.249
0.384
0.158
0.619
0.654
-0.488
0.095
-0.490
-0.827
-0.899
5
-0.180
-0.411
-0.134
-0.609
-0.703
0.665
0.078
0.307
0.647
0.744
-0.957
5
16
TABLE 8S: Microwave Spectrum of the First Excited State of the Lowest Torsion of the
Phosphino Group of Conformer I of 35ClCH2PH2
Watson S-reduction
Total number of transitions:
Transition
4
4
5
5
5
6
7
7
7
7
8
8
8
8
8
8
8
9
9
9
9
9
10
10
10
10
10
10
10
11
11
11
11
11
11
11
11
11
11
12
12
12
12
12
13
14
15
16
16
1
1
0
1
1
0
0
1
2
2
0
2
2
3
3
4
4
0
1
2
3
3
1
2
2
3
3
4
4
0
1
1
2
2
3
3
3
4
4
0
1
2
3
3
0
0
0
0
1
4
3
5
5
4
6
7
6
6
5
8
7
6
6
5
5
4
9
8
7
7
6
9
9
8
8
7
7
6
11
11
10
10
9
9
8
8
8
7
12
12
10
10
9
13
14
15
16
15
5
5
6
6
6
6
7
8
8
8
8
9
9
9
9
9
9
9
10
10
10
10
11
11
11
11
11
11
11
11
12
12
12
12
12
12
12
12
12
12
13
13
13
13
13
14
15
16
16
1
1
0
1
1
1
1
1
2
2
1
2
2
3
3
4
4
1
1
2
3
3
1
2
2
3
3
4
4
1
1
1
2
2
3
3
3
4
4
1
1
2
3
3
1
1
1
1
2
56
obs. frequency
5
4
6
6
5
5
6
7
7
6
7
8
7
7
6
6
5
8
9
8
8
7
10
10
9
9
8
8
7
10
12
11
11
10
10
9
9
9
8
11
13
11
11
10
12
13
14
15
14
29301.990
30400.850
35774.300
35157.560
36476.090
25357.200
26194.080
48618.250
47752.870
47885.210
27172.130
53715.150
53902.690
53769.440
53773.230
53762.720
53762.720
28301.510
60744.860
59930.710
59748.360
59754.360
66801.240
65629.940
65970.420
65728.180
65737.490
65715.740
65715.740
31050.710
70231.570
72852.240
71582.960
72021.820
71709.280
71722.900
71723.840
71693.310
71693.310
32690.270
76064.080
78085.600
77691.120
77711.920
34519.930
36549.080
38786.700
41239.330
59102.980
obs.- weight
calc.
-0.101
0.207
0.087
-0.418
0.163
-0.506
0.223
0.378
-0.451
0.176
-0.115
0.167
0.164
-0.477
0.053
-0.288
-0.309
-0.017
0.029
-0.007
-0.245
0.172
-0.036
-0.153
0.074
-0.194
0.054
0.079
-0.011
0.079
0.101
0.030
-0.007
-0.097
0.073
-0.382
0.558
0.179
0.010
-0.046
-0.051
-0.054
0.067
-0.207
-0.102
-0.163
0.153
0.055
0.030
0.15
0.10
0.10
0.15
0.20
0.25
0.25
0.20
0.25
0.20
0.25
0.10
0.10
0.10
0.15
0.25
0.25
0.25
0.10
0.10
0.10
0.10
0.10
0.15
0.10
0.10
0.10
0.10
0.10
0.25
0.15
0.15
0.15
0.15
0.10
0.10
0.10
0.10
0.10
0.25
0.15
0.10
0.10
0.10
0.25
0.25
0.25
0.25
0.15
t
-0.4
1.4
0.6
-1.8
0.5
-1.3
0.6
1.2
-1.1
0.5
-0.3
1.1
1.1
-3.2
0.2
-0.7
-0.8
-0.0
0.2
-0.0
-1.6
1.1
-0.2
-0.6
0.5
-1.2
0.3
0.6
-0.1
0.2
0.4
0.1
-0.0
-0.4
0.5
-2.5
3.6
1.5
0.1
-0.1
-0.3
-0.5
0.5
-1.6
-0.3
-0.5
0.6
0.7
9.9
distortion corrections
total
fixed
-0.364
-0.545
-1.132
-0.739
-1.051
0.287
0.299
-2.742
-1.360
-1.472
0.198
-2.333
-2.528
-0.495
-0.501
2.169
2.169
-0.072
-5.563
-3.908
-1.575
-1.587
-7.478
-5.150
-5.653
-2.981
-3.003
0.284
0.284
-1.402
-7.312
-9.770
-7.052
-7.809
-4.746
-4.784
-4.784
-1.178
-1.179
-2.637
-9.359
-10.420
-6.903
-6.969
-4.391
-6.785
-9.949
-14.019
16.292
-7.5E-4
-7.8E-4
-2.4E-3
-1.4E-3
-1.4E-3
-0.253
-0.252
-3.7E-3
-4.3E-3
1.5E-3
-0.250
-6.3E-3
1.9E-3
-2.6E-3
-1.8E-3
-1.4E-3
-1.3E-3
-0.247
-7.6E-3
2.3E-3
-4.0E-3
-2.8E-3
-0.010
-0.012
2.7E-3
-5.9E-3
-3.9E-3
-4.1E-3
-4.0E-3
-0.239
-0.011
-0.014
-0.016
2.9E-3
-8.3E-3
-5.2E-3
-5.2E-3
-6.0E-3
-5.9E-3
-0.234
-0.013
3.0E-3
-0.011
-6.6E-3
-0.229
-0.224
-0.219
-0.217
-3.655
17
19
20
21
23
24
25
26
1
1
1
1
1
1
1
18
19
20
22
23
24
25
19
20
21
23
24
25
26
2
2
2
2
2
2
2
17
18
19
21
22
23
24
rms deviation:
57826.580
57673.020
57681.960
58242.960
58819.720
59609.500
60622.160
0.164
-0.026
-0.129
0.033
-0.107
0.013
0.058
0.15
0.15
0.15
0.10
0.15
0.15
0.20
1.1
-0.2
-0.8
9.9
-0.6
0.4
9.9
19.389
19.093
17.823
11.505
5.987
-1.444
-11.061
-3.507
-3.445
-3.375
-3.215
-3.125
-3.027
-2.922
1.6449
Rotational constants (MHz) and kappa:
25949.295
3095.7605
+0.12
0.0069
2875.9843
0.0069
-0.9809497
0.0000007
Inertial constants and defect (uÅ**2):
19.475638
163.24876
+0.000091
0.00036
175.72387
0.00042
-7.00054
0.00034
-0.18065
0.0058
-0.005897
0.0015
Quartic distortion constants:
1.333
-21.081
+0.023
0.29
255.39
fixed
Significant Digits and Correlation Matrix:
8
-0.180
8
0.437
0.518
8
-0.050
0.783
0.789
4
0.497
0.194
0.127
-0.184
5
0.643
-0.471
0.462
0.018
-0.110
5
-0.468
0.447
-0.308
-0.082
0.476
-0.862
4
18
TABLE 9S: Microwave Spectrum of the First Excited State of the Lowest Bending Vibration
of Conformer I of 35ClCH2PH2
Watson S-reduction
Total number of transitions:
Transition
4
4
4
5
5
5
5
6
6
7
7
8
8
9
9
9
9
9
9
9
10
10
10
10
10
10
10
10
10
11
11
11
11
11
11
11
11
11
12
12
12
12
12
12
12
12
12
12
12
0
1
1
0
1
1
2
2
2
1
2
1
2
0
1
2
2
2
3
3
0
1
2
2
3
3
3
4
4
0
1
1
2
3
3
3
4
4
0
1
2
2
3
3
3
4
4
5
5
4
4
3
5
5
4
3
5
5
6
6
7
6
9
8
8
8
7
7
6
10
9
9
8
8
8
7
7
6
11
11
10
9
9
9
8
8
7
12
12
11
10
10
10
9
9
8
8
7
5
5
5
6
6
6
6
7
7
8
8
9
9
9
10
10
10
10
10
10
10
11
11
11
11
11
11
11
11
11
12
12
12
12
12
12
12
12
12
13
13
13
13
13
13
13
13
13
13
0
1
1
0
1
1
2
2
2
1
2
1
2
1
1
2
2
2
3
3
1
1
2
2
3
3
3
4
4
1
1
1
2
3
3
3
4
4
1
1
2
2
3
3
3
4
4
5
5
66
obs. frequency
5
5
4
6
6
5
4
6
6
7
7
8
7
8
9
9
9
8
8
7
9
10
10
9
9
9
8
8
7
10
12
11
10
10
10
9
9
8
11
13
12
11
11
11
10
10
9
9
8
29798.000
29285.620
30358.640
35740.760
35138.340
36425.470
35841.520
41748.300
41748.300
48551.320
47706.520
54608.930
53844.630
27785.330
60661.970
59616.150
59616.150
59865.210
59687.980
59693.540
29043.150
66710.660
65566.370
65896.790
65661.960
65661.190
65670.560
65648.610
65648.610
30466.360
70194.830
72753.990
71940.000
71636.440
71635.730
71649.430
71620.230
71620.230
32065.070
76025.120
77457.640
77994.930
77611.700
77611.350
77632.430
77592.000
77592.000
77581.920
77581.920
obs.- weight
calc.
-0.193
-0.375
0.174
0.050
-0.429
0.029
0.022
-0.083
-0.083
0.324
-0.156
0.360
0.073
0.022
0.006
0.072
0.072
0.139
-0.153
0.026
0.186
0.058
-0.249
0.119
0.337
-0.433
0.203
-0.169
-0.255
0.054
-0.152
0.111
0.144
0.319
-0.391
-0.259
0.271
0.109
-0.036
0.079
-0.340
0.076
0.121
-0.229
0.537
0.066
-0.221
-0.199
-0.201
0.10
0.20
0.10
0.10
0.20
0.20
0.10
0.10
0.10
0.15
0.20
0.10
0.15
0.25
0.10
0.10
0.10
0.10
0.10
0.10
0.25
0.10
0.10
0.10
0.15
0.10
0.10
0.10
0.10
0.25
0.20
0.15
0.15
0.10
0.10
0.10
0.10
0.10
0.25
0.15
0.10
0.10
0.10
0.15
0.15
0.15
0.15
0.15
0.15
t
-1.2
-1.1
1.1
0.3
-1.2
0.1
0.1
-0.5
-0.5
1.3
-0.4
2.2
0.3
0.1
0.0
0.4
0.4
0.8
-0.9
0.2
0.5
0.4
-1.5
0.7
1.3
-2.5
1.2
-1.1
-1.6
0.1
-0.4
0.4
0.6
1.9
-2.3
-1.5
1.7
0.7
-0.1
0.4
-2.7
0.6
0.8
-0.9
2.1
0.3
-0.9
-0.9
-0.9
distortion corrections
total
fixed
-0.690
-0.444
-0.602
-1.186
-0.856
-1.130
-0.389
-0.946
-0.946
-2.883
-1.746
-4.179
-2.932
-0.205
-5.800
-4.172
-4.172
-4.384
-2.502
-2.506
-0.673
-7.780
-5.860
-6.208
-4.054
-4.054
-4.063
-1.380
-1.380
-1.423
-7.982
-10.150
-8.448
-5.981
-5.981
-6.000
-3.057
-3.057
-2.537
-10.197
-10.339
-11.150
-8.316
-8.316
-8.352
-5.141
-5.141
-1.083
-1.083
-1.4E-3
-7.4E-4
-7.7E-4
-2.4E-3
-1.3E-3
-1.4E-3
8.5E-4
-2.7E-3
-2.7E-3
-3.7E-3
-4.2E-3
-5.4E-3
1.9E-3
-0.247
-7.5E-3
-8.7E-3
-8.7E-3
2.3E-3
-4.0E-3
-2.8E-3
-0.243
-0.010
-0.012
2.7E-3
-5.8E-3
-5.8E-3
-3.9E-3
-4.0E-3
-4.0E-3
-0.239
-0.011
-0.014
2.9E-3
-8.2E-3
-8.2E-3
-5.1E-3
-5.9E-3
-5.8E-3
-0.234
-0.013
-0.020
2.9E-3
-0.011
-0.011
-6.5E-3
-8.2E-3
-8.0E-3
-6.4E-3
-6.4E-3
19
12
12
13
14
16
18
19
20
20
21
21
22
23
24
25
26
27
6
6
0
0
0
1
1
0
1
0
1
1
1
1
1
1
1
7
6
13
14
16
17
18
20
19
21
20
21
22
23
24
25
26
13
13
13
14
16
18
19
20
20
21
21
22
23
24
25
26
27
6
6
1
1
1
2
2
1
2
1
2
2
2
2
2
2
2
8
7
12
13
15
16
17
19
18
20
19
20
21
22
23
24
25
rms deviation:
77580.040
77580.040
33848.970
35827.130
40399.750
57170.300
56866.450
52146.650
56705.980
55629.520
56702.770
56871.140
57224.000
57773.200
58528.930
59502.580
60701.990
0.312
0.312
-0.073
-0.230
0.117
0.282
-0.169
0.190
0.056
-0.294
-0.114
-0.227
-0.190
0.028
-0.278
0.259
0.298
0.15
0.15
0.25
0.25
0.25
0.10
0.10
0.25
0.15
0.25
0.15
0.20
0.15
0.25
0.25
0.25
0.25
2.4
2.4
-0.2
-0.8
0.4
9.9
9.9
9.9
0.3
9.9
-0.5
-0.7
-1.2
0.1
-0.8
1.2
9.9
3.861
3.861
-4.111
-6.252
-12.708
16.133
16.747
-37.805
16.728
-47.288
15.912
14.121
11.162
6.829
0.899
-6.862
-16.701
-4.1E-3
-4.1E-3
-0.229
-0.224
-0.217
-3.567
-3.511
-0.247
-3.450
-0.274
-3.381
-3.305
-3.222
-3.133
-3.036
-2.932
-2.822
1.8129
Rotational constants (MHz) and kappa:
25559.762
3090.2216
+0.093
0.0061
2875.6672
0.0063
-0.9810833
0.0000005
Inertial constants and defect (uÅ**2):
19.772449
163.54137
+0.000072
0.00032
175.74324
0.00038
-7.57058
0.00030
Quartic distortion constants:
1.392
-17.23
+0.022
0.20
-0.158236
0.0033
0.002988
0.00083
255.39
fixed
Significant Digits and Correlation Matrix:
8
-0.235
8
0.225
0.575
8
-0.217
0.833
0.794
4
0.647
-0.162
-0.060
-0.432
4
0.519
-0.422
0.469
-0.024
0.128
6
-0.433
0.229
-0.342
-0.147
0.298
-0.653
4
20
TABLE 10S: Microwave
37
ClCH2PH2
Spectrum of the Ground Vibrational State
of Conformer I of
Watson S-reduction
Total number of transitions: 141
Transition
4
4
4
5
5
5
5
6
6
6
6
6
6
6
7
7
7
7
7
8
8
8
8
8
9
9
9
9
9
9
9
9
9
9
9
9
10
10
10
10
10
10
10
10
10
10
10
11
11
0
1
1
0
1
1
2
0
0
1
1
2
2
3
0
1
2
2
3
1
1
2
2
3
0
1
0
1
2
2
3
3
4
4
5
5
0
1
1
0
1
2
2
3
3
4
4
0
1
4
4
3
5
5
4
3
6
6
6
5
5
4
4
7
6
6
5
4
7
7
7
6
6
9
8
9
8
8
7
7
6
6
5
5
4
10
10
9
10
9
9
8
8
7
7
6
11
11
5
5
5
6
6
6
6
6
7
7
7
7
7
7
7
7
8
8
8
8
9
9
9
9
9
9
10
10
10
10
10
10
10
10
10
10
10
10
10
11
11
11
11
11
11
11
11
11
11
0
1
1
0
1
1
2
1
0
1
1
2
2
3
1
2
2
2
3
2
1
2
2
3
1
2
0
1
2
2
3
3
4
4
5
5
1
2
2
0
1
2
2
3
3
4
4
1
2
obs. frequency
5
5
4
6
6
5
4
5
7
7
6
6
5
5
6
5
7
6
5
6
8
8
7
7
8
7
10
9
9
8
8
7
7
6
6
5
9
9
8
11
10
10
9
9
8
8
7
10
10
29110.260
28613.680
29650.760
34916.100
34332.640
35576.650
35009.940
24944.170
40713.790
40048.960
41500.060
40783.140
40862.540
40806.420
25730.430
65358.650
46603.600
46722.680
46640.300
64660.550
53337.530
52422.420
52591.840
52472.220
27710.150
63914.840
58040.960
59250.890
58238.830
58470.540
58305.780
58311.040
58297.100
58297.100
58294.980
58294.980
28918.960
73829.350
63134.560
63791.500
65159.440
64052.250
64359.730
64140.950
64149.020
64129.520
64129.520
30286.760
74994.430
obs.- weight
calc.
0.299
-0.272
0.015
0.062
0.001
0.134
0.008
-0.021
0.286
-0.185
0.214
0.233
0.251
-0.327
-0.103
0.272
-0.101
0.159
-0.140
-0.069
0.186
0.056
0.244
0.227
0.317
-0.031
-0.269
0.349
0.198
0.171
-0.267
0.180
-0.197
-0.234
0.116
0.116
-0.185
-0.268
-0.139
-0.274
0.096
0.005
0.186
-0.137
0.121
0.025
-0.049
0.045
-0.109
0.15
0.15
0.15
0.10
0.20
0.20
0.10
0.25
0.10
0.25
0.20
0.10
0.10
0.10
0.25
0.25
0.10
0.15
0.15
0.25
0.20
0.10
0.10
0.10
0.25
0.25
0.10
0.10
0.10
0.10
0.10
0.10
0.15
0.15
0.10
0.10
0.25
0.25
0.25
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.25
0.25
t
1.2
-1.1
0.1
0.4
0.0
0.4
0.0
-0.0
1.7
-0.4
0.6
1.4
1.5
-1.9
-0.2
0.6
-0.6
0.6
-0.5
-0.2
0.5
0.3
1.5
1.4
0.8
-0.1
-1.6
2.1
1.2
1.0
-1.6
1.1
-0.8
-0.9
0.7
0.7
-0.5
-0.7
-0.3
-1.7
0.6
0.0
1.1
-0.8
0.7
0.2
-0.3
0.1
-0.3
distortion corrections
total
fixed
-0.620
-0.350
-0.515
-1.065
-0.705
-0.990
-0.173
0.238
-1.680
-1.214
-1.667
-0.637
-0.674
0.703
0.251
-0.193
-1.325
-1.399
0.196
0.985
-3.754
-2.250
-2.386
-0.552
-0.082
2.353
-4.770
-5.226
-3.440
-3.673
-1.576
-1.582
1.134
1.134
4.611
4.611
-0.538
0.424
3.905
-6.282
-7.025
-4.923
-5.300
-2.906
-2.918
0.080
0.080
-1.280
0.780
21
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
13
13
14
14
15
15
15
16
16
16
17
18
19
19
20
21
22
22
23
23
23
25
25
25
26
26
27
27
27
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
0
1
1
2
3
4
4
9
9
10
10
11
11
12
12
0
1
0
1
3
3
0
3
3
0
3
3
3
3
3
3
3
4
4
4
3
4
4
3
4
4
4
4
3
11
10
10
9
9
8
8
7
7
6
6
5
5
4
4
3
3
2
12
12
11
10
10
9
8
4
3
3
2
2
1
1
0
13
12
14
13
13
12
15
14
13
16
14
15
17
16
17
18
20
19
20
19
21
22
21
22
23
22
24
23
24
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
14
14
14
14
15
15
15
16
16
17
18
18
19
20
21
21
22
22
24
24
24
26
25
25
26
26
28
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
1
1
1
2
3
4
4
9
9
10
10
11
11
12
12
1
2
1
2
4
4
1
4
4
1
4
4
4
4
4
4
4
5
5
5
2
5
5
2
5
5
5
5
2
12
11
11
10
10
9
9
8
8
7
7
6
6
5
5
4
4
3
11
13
12
11
11
10
9
5
4
4
3
3
2
2
1
12
11
13
12
10
11
14
11
12
15
13
14
14
15
16
17
17
16
17
18
22
19
20
25
20
21
21
22
27
68588.830
71063.400
69862.830
70259.470
69976.900
69989.390
69962.410
69962.410
69956.080
69956.080
69956.080
69956.080
69959.050
69959.050
69964.250
69964.250
69970.710
69970.710
31821.650
74286.330
76961.520
76170.800
75813.770
75795.940
75795.940
75800.390
75800.390
75808.770
75808.770
75818.450
75818.450
75829.050
75829.050
33533.430
60740.500
35430.860
59980.220
71193.810
71080.890
37522.150
65330.670
65165.300
39814.550
59228.870
53265.950
47726.140
47273.340
41245.370
35176.050
30127.960
75532.210
69638.400
69590.370
39251.800
57826.580
57734.340
28953.670
51908.270
51783.290
45981.720
45813.250
37269.380
0.224
0.205
-0.112
-0.159
-0.199
0.155
0.022
-0.117
-0.309
-0.310
-0.042
-0.042
0.079
0.079
0.368
0.368
0.342
0.342
-0.125
0.174
0.015
-0.096
-0.277
-0.094
-0.341
-0.171
-0.171
-0.067
-0.067
0.007
0.007
-0.224
-0.224
-0.112
-0.223
-0.047
-0.190
-0.173
0.056
0.059
-0.137
-0.223
0.258
0.260
-0.131
-0.319
-0.047
-0.039
-0.379
-0.331
0.066
0.081
-0.133
-0.244
-0.137
-0.196
-0.346
-0.233
0.265
-0.184
0.125
-0.102
0.20
0.10
0.20
0.10
0.10
0.10
0.10
0.10
0.25
0.25
0.25
0.25
0.15
0.15
0.25
0.25
0.15
0.15
0.25
0.10
0.20
0.10
0.10
0.10
0.10
0.20
0.20
0.15
0.15
0.15
0.15
0.25
0.25
0.25
0.25
0.25
0.25
0.10
0.10
0.25
0.10
0.10
0.25
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.20
0.10
0.10
0.20
0.10
0.10
0.10
0.10
0.10
0.7
1.3
-0.3
-1.0
-1.2
0.9
0.1
-0.7
-0.7
-0.7
-0.1
-0.1
0.3
0.3
0.9
0.9
1.4
1.4
-0.3
1.1
0.0
-0.6
-1.7
-0.6
-2.1
-0.5
-0.5
-0.3
-0.3
0.0
0.0
-0.6
-0.6
-0.3
-0.5
-0.1
-0.5
-1.1
0.4
0.2
-0.9
-1.4
1.1
1.6
-0.8
-2.0
-0.3
-0.3
-2.7
-2.3
0.4
0.5
-0.9
-0.9
-0.9
-1.2
-1.3
-1.4
1.6
-1.1
0.8
9.9
-6.920
-9.180
-6.727
-7.308
-4.574
-4.596
-1.310
-1.310
2.870
2.870
7.967
7.967
13.986
13.986
20.929
20.929
28.796
28.796
-2.396
-8.856
-11.717
-9.739
-6.611
-3.067
-3.067
29.562
29.562
39.087
39.087
49.614
49.614
61.143
61.143
-3.982
9.480
-6.149
11.510
-4.841
-4.572
-9.018
2.594
3.045
-12.717
11.535
20.968
29.645
31.422
42.991
55.781
64.262
26.427
41.555
41.915
-148.096
75.259
76.090
-84.619
93.915
95.144
113.825
115.615
-89.486
22
28
28
28
29
30
30
33
33
34
34
36
37
38
38
41
41
42
43
43
46
47
48
48
49
49
50
50
53
54
58
4
4
3
4
4
4
5
5
5
5
5
5
5
5
6
6
6
6
6
7
7
7
7
7
7
7
7
8
8
8
25
24
25
25
27
26
29
28
30
29
32
33
34
33
36
35
37
38
37
40
40
42
41
43
42
44
43
46
46
50
27
27
29
28
29
29
32
32
33
33
35
36
37
37
40
40
41
42
42
45
46
47
47
48
48
49
49
52
53
57
5
5
2
5
5
5
6
6
6
6
6
6
6
6
7
7
7
7
7
8
8
8
8
8
8
8
8
9
9
9
22
23
28
24
24
25
26
27
27
28
29
30
31
32
33
34
34
35
36
37
39
39
40
40
41
41
42
43
45
49
rms deviation:
40047.100
39822.400
41110.790
33808.240
28153.540
27767.890
56238.430
56206.460
50300.300
50257.140
38394.340
32425.800
26446.500
26318.090
54722.090
54711.600
48779.480
42827.590
42809.320
71069.760
65152.340
59231.960
59228.870
53302.140
53298.490
47364.420
47360.320
75645.450
69743.930
46079.120
0.098
-0.086
0.130
-0.225
0.076
-0.199
0.156
0.372
0.235
0.250
0.245
0.104
-0.189
-0.015
0.332
0.355
0.245
-0.018
0.146
-0.005
-0.004
0.270
-0.351
0.209
-0.163
-0.161
0.065
-0.249
-0.140
-0.233
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.15
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.15
0.6
-0.6
9.9
-1.5
0.5
-1.4
1.0
2.3
1.4
1.5
1.5
0.7
-1.4
-0.1
2.0
2.2
1.5
-0.1
0.9
-0.0
-0.0
1.7
-2.3
1.4
-1.1
-1.2
0.5
-5.5
-1.4
-1.8
135.025
137.594
-89.124
161.184
181.420
186.503
209.478
210.114
241.294
242.203
310.098
347.188
386.136
389.551
437.225
437.611
485.683
536.301
537.051
591.594
652.849
716.303
716.449
782.335
782.536
850.905
851.183
929.134
1009.827
1360.949
1.7230
Rotational constants (MHz) and kappa:
25602.1098
3017.60892
2810.19168
+0.013
0.0020
0.0027
Inertial constants and defect (uÅ**2):
19.7397434
167.476664
+0.000010
0.00011
Quartic distortion constants:
1.25218
-19.2676
+0.0028
0.035
-0.9817991
0.0000003
179.837938
0.00018
-7.37847
0.00020
-0.165063
0.0026
0.000668
0.0010
258.535
0.37
Significant Digits and Correlation Matrix:
9
0.686
9
0.610
0.054
9
0.624
0.184
0.775
6
0.533
0.537
0.406
0.637
6
0.257
-0.235
0.323
0.404
-0.376
6
0.204
-0.372
0.679
0.684
-0.031
0.621
6
-0.255
0.207
-0.519
-0.688
0.014
-0.655
-0.942
3
23
TABLE 11S: Microwave Spectrum of the First Excited State of the Lowest Torsion of the
Phosphino Group of Conformer I of 37ClCH2PH2
Watson S-reduction
Total number of transitions:
Transition
7
8
8
9
9
9
9
9
9
10
10
10
10
10
11
11
11
11
11
11
12
12
12
3 5 8
3 6 9
3 5 9
1 8 10
2 7 10
3 7 10
3 6 10
4 6 10
4 5 10
1 9 11
3 8 11
3 7 11
4 7 11
4 6 11
1 10 12
2 10 12
3 9 12
3 8 12
4 8 12
4 7 12
3 9 13
4 9 13
4 8 13
3
3
3
1
2
3
3
4
4
1
3
3
4
4
1
2
3
3
4
4
3
4
4
23
obs. frequency
6
7
6
9
8
8
7
7
6
10
9
8
8
7
11
11
10
9
9
8
10
10
9
rms deviation:
46596.710
52424.270
52427.260
59209.530
58419.930
58252.760
58258.030
58244.400
58244.400
65113.660
64082.830
64090.990
64071.460
64071.460
71012.830
69797.500
69913.510
69926.110
69899.050
69899.050
75764.230
75727.530
75727.530
obs.- weight
calc.
0.270
-0.005
0.118
0.296
-0.082
-0.334
0.024
-0.005
-0.043
0.023
-0.084
0.103
0.099
0.023
-0.178
-0.007
-0.214
0.001
0.023
-0.120
0.202
0.070
-0.183
0.20
0.15
0.15
0.20
0.10
0.15
0.10
0.20
0.20
0.10
0.10
0.10
0.10
0.10
0.15
0.10
0.15
0.15
0.10
0.10
0.10
0.15
0.15
t
1.1
-0.0
0.7
1.3
9.9
-1.9
0.2
-0.0
-0.2
0.6
-0.7
0.9
0.9
0.2
-1.4
9.9
-1.2
0.0
0.2
-1.1
2.9
0.4
-1.1
distortion corrections
total
fixed
0.421
-0.309
-0.312
-5.245
-3.592
-1.317
-1.323
1.638
1.638
-7.058
-2.634
-2.646
0.621
0.621
-9.230
-6.652
-4.293
-4.315
-0.734
-0.735
-6.365
-2.462
-2.462
-0.012
-0.020
-0.022
-0.611
-0.182
-0.032
-0.037
-0.020
-0.020
-0.795
-0.050
-0.059
-0.032
-0.032
-1.007
0.067
-0.073
-0.092
-0.048
-0.048
-0.137
-0.070
-0.070
1.1530
Rotational constants (MHz) and kappa:
25807
3016.2653
+11
0.012
2806.1654
0.018
-0.981731
0.000010
Inertial constants and defect (uÅ**2):
19.583
167.55127
+0.008
0.00068
180.09597
0.0012
-7.0384
0.0082
-0.1651
fixed
0.00067
fixed
Quartic distortion constants:
1.266
-21.01
+0.028
0.33
258.54
fixed
Significant Digits and Correlation Matrix:
5
-0.104
8
0.265
-0.515
8
0.178
0.498
0.404
4
-0.094
-0.419
0.563
-0.180
4
24
TABLE 12S: Microwave Spectrum of the
Vibration of Conformer I of 37ClCH2PH2
First
Excited
State
of
the
Lowest
Bending
Watson S-reduction
Total number of transitions:
Transition
8
8
8
9
9
9
9
9
9
10
10
10
10
10
11
11
11
11
11
11
11
12
12
12
12
12
12
12
2
3
3
1
2
3
3
5
5
1
2
2
3
3
1
2
2
3
3
4
4
2
3
3
4
4
5
5
7
6
5
8
7
7
6
5
4
9
9
8
8
7
10
10
9
9
8
8
7
10
10
9
9
8
8
7
9
9
9
10
10
10
10
10
10
11
11
11
11
11
12
12
12
12
12
12
12
13
13
13
13
13
13
13
2
3
3
1
2
3
3
5
5
1
2
2
3
3
1
2
2
3
3
4
4
2
3
3
4
4
5
5
rms deviation:
28
obs. frequency
8
7
6
9
8
8
7
6
5
10
10
9
9
8
11
11
10
10
9
9
8
11
11
10
10
9
9
8
52321.020
52369.260
52372.320
59126.220
58353.530
58192.000
58197.000
58179.980
58179.980
65022.920
63928.600
64230.600
64015.540
64023.430
70914.700
69728.090
70117.770
69840.020
69852.160
69825.240
69825.240
76016.310
75665.340
75683.730
75647.410
75647.410
75638.270
75638.270
obs.- weight
calc.
0.017
-0.232
0.086
-0.027
-0.205
-0.074
0.229
-0.192
-0.192
0.026
-0.066
0.111
-0.079
0.186
0.024
-0.230
-0.200
-0.097
0.198
0.079
-0.056
-0.142
-0.190
0.462
0.133
-0.106
-0.117
-0.119
0.20
0.15
0.15
0.10
0.20
0.10
0.10
0.25
0.25
0.10
0.10
0.10
0.10
0.10
0.15
0.10
0.15
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.15
0.15
t
0.1
-1.1
0.4
-2.3
-0.7
-0.6
1.8
-0.5
-0.5
9.9
-0.7
1.2
-0.5
1.3
0.2
-4.9
-1.1
-0.7
1.3
0.6
-0.4
9.9
-1.6
3.8
1.1
-0.9
-0.7
-0.7
distortion corrections
total
fixed
-2.489
-1.076
-1.078
-5.305
-3.935
-2.160
-2.166
3.009
3.009
-7.115
-5.222
-5.589
-3.552
-3.563
-9.283
-7.057
-7.623
-5.281
-5.303
-2.551
-2.551
-10.079
-7.380
-7.419
-4.415
-4.416
-0.625
-0.625
0.011
-0.020
-0.022
-0.611
-0.181
-0.032
-0.036
-0.013
-0.013
-0.796
0.040
-0.289
-0.049
-0.058
-1.008
0.067
-0.442
-0.072
-0.090
-0.047
-0.048
-0.649
-0.103
-0.136
-0.069
-0.070
-0.047
-0.047
1.6243
Rotational constants (MHz) and kappa:
25462.5
3010.7224
+7.9
0.014
2805.791
0.018
-0.981910
0.000006
Inertial constants and defect (uÅ**2):
19.8480
167.85974
+0.0061
0.00078
180.1200
0.0011
-7.5878
0.0066
-0.1651
fixed
0.00067
fixed
Quartic distortion constants:
1.255
-16.09
+0.033
0.32
258.54
fixed
25
Significant Digits and Correlation Matrix:
6
0.023
8
-0.218
-0.412
7
-0.289
0.608
0.399
4
0.098
-0.493
0.416
-0.382
4
26
TABLE 13S: Microwave Spectrum of the Ground Vibrational State of Conformer II of
35
ClCH2PH2
Watson S-reduction
Total number of transitions:
Transition
3
4
4
4
5
5
5
5
5
5
6
6
6
6
7
7
7
7
7
8
8
8
8
8
8
8
8
8
9
9
9
9
9
9
10
10
10
10
10
10
10
10
11
11
11
11
11
11
11
11
0
0
1
1
1
0
1
1
2
2
0
0
2
2
0
1
1
2
2
0
1
1
0
1
2
2
3
3
0
1
0
1
2
2
0
1
0
1
1
1
2
2
0
1
1
0
1
1
1
2
3
4
4
3
5
5
5
4
4
3
6
6
5
4
7
6
6
6
5
8
8
7
8
7
7
6
6
5
9
8
9
8
8
7
10
9
10
10
10
9
9
8
11
11
10
11
11
11
10
10
4
5
5
5
5
6
6
6
6
6
6
7
7
7
7
7
8
8
8
8
8
8
9
9
9
9
9
9
9
9
10
10
10
10
10
10
11
11
11
11
11
11
11
11
11
12
12
12
12
12
0
0
1
1
2
0
1
1
2
2
1
0
2
2
1
2
1
2
2
1
2
2
0
1
2
2
3
3
1
2
0
1
2
2
1
2
0
0
1
1
2
2
1
2
2
0
0
1
1
2
85
obs. frequency
4
5
5
4
4
6
6
5
5
4
5
7
6
5
6
5
7
7
6
7
7
6
9
8
8
7
7
6
8
7
10
9
9
8
9
8
11
11
11
10
10
9
10
10
9
12
12
12
11
11
24743.100
30910.640
30297.680
31597.680
66643.800
37066.700
36350.400
37909.900
37139.520
37221.552
24421.230
43208.590
43322.700
43453.950
25430.630
61373.820
50521.380
49502.890
49698.800
26617.900
69412.540
60551.340
55441.460
56819.040
55679.820
55958.040
55760.710
55766.340
27994.800
59690.780
61529.880
63110.400
61852.820
62232.580
29575.350
58811.860
67596.770
52294.450
66553.700
69394.150
68021.370
68523.130
31372.270
73403.710
57941.180
73642.740
59383.830
72578.510
75669.330
74185.030
obs.- weight
calc.
0.164
-0.119
-0.213
0.206
-0.071
-0.026
-0.399
0.144
0.109
0.093
-0.075
-0.016
-0.018
0.269
-0.052
-0.152
-0.001
-0.096
0.073
0.145
0.112
0.022
-0.498
-0.086
0.033
0.048
0.241
-0.248
-0.123
0.596
-0.101
0.058
0.127
0.013
0.067
-0.550
-0.428
0.103
0.190
0.057
0.086
-0.017
0.092
0.135
-0.283
-0.175
0.079
-0.440
-0.047
-0.111
0.10
0.10
0.10
0.10
0.20
0.10
0.15
0.15
0.10
0.10
0.25
0.15
0.15
0.15
0.25
0.30
0.15
0.10
0.10
0.25
0.25
0.30
0.15
0.10
0.10
0.10
0.15
0.15
0.25
0.25
0.15
0.10
0.10
0.10
0.25
0.30
0.15
0.25
0.15
0.20
0.10
0.10
0.25
0.30
0.25
0.10
0.25
0.15
0.15
0.10
t
1.2
-0.9
-1.6
1.6
-0.3
-0.2
-1.9
0.7
0.8
0.7
-0.2
-0.1
-0.1
1.3
-0.2
-0.4
-0.0
-0.7
0.6
0.4
0.4
0.1
-2.4
-0.6
0.2
0.4
1.2
-1.2
-0.4
1.8
-0.5
0.4
0.9
0.1
0.2
-1.4
-2.1
0.3
0.9
0.2
0.6
-0.1
0.3
0.3
-0.9
-1.4
0.3
-2.2
-0.2
-0.9
distortion corrections
total
fixed
-0.460
-0.892
-0.528
-0.779
-2.450
-1.529
-1.042
-1.474
-0.358
-0.404
0.265
-2.406
-1.071
-1.165
0.210
0.339
-3.785
-2.081
-2.261
-0.023
-0.378
1.863
-4.997
-5.491
-3.430
-3.748
-1.276
-1.286
-0.517
3.606
-6.764
-7.621
-5.158
-5.684
-1.374
5.543
-8.874
-13.520
-7.591
-10.215
-7.302
-8.131
-2.715
1.003
7.627
-11.348
-17.277
-9.928
-13.313
-9.902
27
11
11
11
12
12
12
12
13
13
13
13
14
14
15
15
16
17
18
19
19
20
21
21
22
22
23
24
24
25
26
27
28
29
30
31
2
3
3
0
1
1
1
0
1
1
1
0
1
0
1
1
1
1
0
1
0
0
1
0
1
0
0
1
1
1
1
1
1
1
1
9
9
8
12
11
12
12
13
13
12
13
14
13
15
14
15
16
17
19
18
20
21
20
22
21
23
24
23
24
25
26
27
28
29
30
12
12
12
12
12
13
13
13
13
13
14
14
14
15
15
16
17
18
19
19
20
21
21
22
22
23
24
24
25
26
27
28
29
30
31
2
3
3
1
2
0
1
1
2
2
0
1
2
1
2
2
2
2
1
2
1
1
2
1
2
1
1
2
2
2
2
2
2
2
2
rms deviation:
10
10
9
11
10
13
13
12
12
11
14
13
12
14
13
14
15
16
18
17
19
20
19
21
20
22
23
22
23
24
25
26
27
28
29
74830.070
74370.000
74396.290
33398.660
57101.310
66472.140
78598.770
35666.780
76754.770
56319.550
73542.970
38187.110
55619.480
40967.970
55027.340
54566.720
54261.140
54132.750
54748.730
54200.920
58840.030
63168.410
54999.360
67718.450
55762.100
72470.280
77401.740
58081.860
59663.960
61540.780
63720.580
66210.700
69012.610
72128.290
75555.750
0.137
0.133
0.050
0.020
-0.709
0.346
0.078
0.009
-0.160
0.088
-0.024
0.044
0.127
0.221
0.442
0.261
-0.030
0.093
0.094
0.007
0.270
-0.104
-0.129
0.023
0.250
0.098
-0.438
-0.552
-0.571
-0.694
-0.804
0.298
0.320
0.229
0.125
0.10
0.10
0.10
0.25
0.20
0.25
0.10
0.25
0.25
0.15
0.25
0.25
0.25
0.25
0.15
0.15
0.15
0.15
0.25
0.15
0.25
0.25
0.15
0.25
0.15
0.25
0.25
0.15
0.30
0.40
0.40
0.25
0.25
0.25
0.25
1.1
1.1
0.4
0.1
-2.7
1.2
0.7
0.0
-0.5
0.5
-0.1
0.1
0.4
0.7
2.4
1.4
-0.2
0.5
0.3
0.0
0.9
-0.3
-0.7
0.1
1.5
0.4
-2.9
-3.4
-1.4
-1.3
-1.5
1.0
1.1
0.9
0.9
-11.150
-7.268
-7.344
-4.681
9.790
-21.553
-12.681
-7.426
0.716
11.937
-26.336
-11.119
13.946
-15.934
15.669
16.931
17.533
17.253
-49.632
15.845
-62.287
-76.764
8.554
-93.055
2.066
-111.103
-130.807
-18.266
-32.828
-50.811
-72.572
-98.442
-128.704
-163.575
-203.188
1.4096
Rotational constants (MHz) and kappa:
24658.174
3225.87366
2965.85156
+0.14
0.0044
0.0042
Inertial constants and defect (uÅ**2):
20.495398
156.664250
+0.00011
0.00021
Quartic distortion constants:
1.810
-24.97
+0.017
0.21
298.3
29
-0.9760263
0.0000003
170.399316
0.00024
-6.76033
0.00014
-0.250414
0.00098
-0.006301
0.00040
28
Significant Digits and Correlation Matrix:
8
-0.160
9
0.052
0.839
9
-0.115
0.885
0.900
4
-0.063
0.285
-0.002
0.011
4
0.942
-0.247
0.013
-0.134
-0.348
4
0.326
-0.347
0.195
-0.056
-0.427
0.390
6
0.089
0.262
-0.102
-0.004
0.644
-0.045
-0.701
4
29
TABLE 14S: Microwave Spectrum of the First Excited Torsional State of Conformer II of
35
ClCH2PH2
Watson S-reduction
Total number of transitions:
Transition
4
5
5
5
6
7
8
8
8
8
8
9
9
9
10
10
10
10
11
12
1 4 5
0 5 6
1 5 6
1 4 6
0 6 7
0 7 8
0 8 9
5 4 9
5 3 9
6 3 9
6 2 9
0 9 10
1 9 10
2 8 10
1 10 11
1 9 11
4 7 11
4 6 11
1 10 12
1 12 13
1
0
1
1
0
0
0
5
5
6
6
0
1
2
1
1
4
4
1
1
20
obs. frequency
5
6
6
5
7
8
9
5
4
4
3
10
10
9
11
10
8
7
11
13
rms deviation:
30201.310
36937.980
36234.440
37763.950
43059.900
49166.370
55255.160
55548.200
55548.200
55549.700
55549.700
61324.140
60331.020
61634.600
66343.660
69130.020
67903.520
67903.520
75382.520
78352.000
obs.- weight
calc.
0.309
-0.167
-0.299
0.173
-0.005
0.310
0.371
-0.107
-0.107
0.135
0.135
-0.405
-0.032
-0.506
0.231
-0.041
0.054
-0.143
0.020
0.026
0.10
0.10
0.10
0.10
0.20
0.20
0.20
0.20
0.20
0.20
0.20
0.20
0.15
0.20
0.15
0.15
0.15
0.15
0.10
0.10
t
3.2
-1.5
-4.3
9.9
-0.0
1.1
1.8
-0.4
-0.4
1.5
1.5
9.9
-0.2
-1.5
1.2
-0.3
0.4
-1.0
9.9
9.9
distortion corrections
total
fixed
-0.586
-1.622
-1.140
-1.572
-2.554
-3.774
-5.314
5.414
5.414
10.270
10.270
-7.201
-6.077
-5.623
-8.172
-10.798
-1.654
-1.655
-14.070
-13.638
0.127
0.029
0.221
-0.211
0.066
0.131
0.239
-0.014
-0.014
-7.5E-3
-7.5E-3
0.405
1.086
0.075
1.471
-1.161
-0.062
-0.062
-1.454
2.520
1.7455
Rotational constants (MHz) and kappa:
24660
3212.406
+20
0.013
2957.3777
0.012
-0.97650
0.00002
Inertial constants and defect (uÅ**2):
20.494
157.3210
+0.016
0.0006
170.88757
0.00067
-6.927
0.016
-0.25041
fixed
-0.0063
fixed
Quartic distortion constants:
1.917
-24.49
+0.034
0.42
298.3
fixed
Significant Digits and Correlation Matrix:
5
-0.394
7
-0.311
0.225
8
0.200
0.457
0.648
4
-0.649
0.502
0.310
-0.033
4
30
TABLE 15S: Microwave Spectrum of the Ground Vibrational State of Conformer II of
37
ClCH2PH2
Watson S-reduction
Total number of transitions:
Transition
4
4
5
5
5
5
6
7
7
7
7
7
8
8
8
8
8
9
9
9
9
10
10
10
10
11
11
11
11
11
11
11
11
12
12
12
13
13
14
14
15
16
16
17
18
19
20
21
22
0
1
0
1
1
2
0
0
0
1
2
2
0
0
1
2
2
0
2
2
3
0
0
1
2
0
1
0
1
1
2
3
3
0
1
2
0
1
0
1
0
0
1
1
1
1
1
1
0
4
4
5
5
4
4
6
7
7
6
6
5
8
8
7
7
6
9
8
7
6
10
10
9
9
11
10
11
11
10
10
9
8
12
12
11
13
12
14
13
15
16
15
16
17
18
19
20
22
5
5
6
6
6
6
6
7
8
8
8
8
8
9
9
9
9
9
10
10
10
10
11
11
11
11
11
12
12
12
12
12
12
12
13
13
13
13
14
14
15
16
16
17
18
19
20
21
22
0
1
0
1
1
2
1
1
0
1
2
2
1
0
1
2
2
1
2
2
3
1
0
1
2
1
2
0
1
1
2
3
3
1
1
2
1
2
1
2
1
1
2
2
2
2
2
2
1
58
obs. frequency
5
5
6
6
5
5
5
6
8
7
7
6
7
9
8
8
7
8
9
8
7
9
11
10
10
10
9
12
12
11
11
10
9
11
13
12
12
11
13
12
14
15
14
15
16
17
18
19
21
30146.570
29559.100
36151.920
35464.770
36955.260
36218.660
24286.850
25247.250
48122.140
49250.750
48276.170
48455.260
26375.850
54082.530
55390.340
54300.920
54554.940
27683.300
60321.710
60668.920
60430.570
29182.890
65949.290
67652.990
66338.350
30886.000
58157.240
71853.370
70817.320
73772.970
72350.770
72520.770
72543.170
32805.480
76692.700
78358.660
34952.730
56542.700
37337.940
55830.640
39970.110
42854.750
54715.330
54357.020
54159.720
54141.970
54323.060
54718.620
65392.030
obs.- weight
calc.
0.086
-0.122
0.078
-0.188
0.355
0.324
0.105
-0.050
0.196
0.337
-0.088
0.071
0.081
-0.475
-0.476
0.267
-0.132
-0.280
0.227
-0.153
-0.462
0.024
-0.451
0.036
-0.009
-0.079
-0.172
-0.140
0.031
0.026
-0.131
0.399
-0.241
-0.034
0.236
-0.069
-0.034
-0.138
-0.190
-0.141
0.095
0.387
0.149
0.261
0.359
-0.306
-0.217
-0.033
0.270
0.15
0.10
0.10
0.15
0.15
0.20
0.25
0.25
0.15
0.15
0.10
0.15
0.25
0.15
0.20
0.15
0.20
0.25
0.10
0.15
0.20
0.25
0.15
0.10
0.15
0.25
0.15
0.15
0.10
0.15
0.10
0.15
0.15
0.25
0.10
0.10
0.25
0.20
0.25
0.15
0.25
0.25
0.15
0.10
0.10
0.10
0.10
0.15
0.25
t
0.4
-0.9
0.6
-0.8
1.6
1.0
0.4
-0.2
0.9
1.5
-0.7
0.3
0.2
-2.1
-1.5
1.2
-0.4
-0.8
1.6
-0.7
-1.5
0.1
-1.9
0.3
-0.0
-0.2
9.9
-0.6
0.2
0.1
-1.0
2.0
-1.2
-0.1
2.5
-0.7
-0.1
-0.5
-0.6
-0.8
0.3
1.3
0.7
2.3
2.9
-2.4
-1.7
-0.2
9.9
distortion corrections
total
fixed
-0.832
-0.477
-1.427
-0.951
-1.366
-0.275
0.295
0.252
-3.315
-3.526
-1.863
-2.025
0.042
-4.664
-5.121
-3.112
-3.399
-0.414
-4.715
-5.192
-2.416
-1.214
-8.286
-9.543
-6.708
-2.471
7.889
-10.596
-9.183
-12.444
-9.125
-6.507
-6.572
-4.319
-11.736
-12.002
-6.907
12.263
-10.397
14.359
-14.959
-20.765
17.685
18.567
18.658
17.726
15.519
11.764
-89.356
31
22
23
23
24
25
26
27
28
29
1
0
1
1
1
1
1
1
1
21
23
22
23
24
25
26
27
28
22
23
23
24
25
26
27
28
29
2
1
2
2
2
2
2
2
2
20
22
21
22
23
24
25
26
27
rms deviation:
55343.270
69936.420
56211.030
57333.170
58723.080
60388.770
62339.540
64582.000
67121.590
-0.032
-0.311
0.197
-0.480
0.117
0.046
0.065
-0.102
0.055
0.10
0.25
0.15
0.20
0.15
0.15
0.10
0.10
0.10
-0.3
9.9
0.9
-1.6
0.6
0.2
0.6
-1.3
9.9
6.164
-107.062
-1.600
-11.863
-24.978
-41.306
-61.205
-85.018
-113.053
1.6339
Rotational constants (MHz) and kappa:
24578.779
3143.27413
2894.77209
+0.28
0.0074
0.0069
Inertial constants and defect (uÅ**2):
20.561602
160.781102
+0.00023
0.00038
Quartic distortion constants:
1.689
-24.547
+0.025
0.54
-0.9770797
0.0000008
174.583373
0.00042
-6.75933
0.00021
-0.240629
0.0023
-0.004721
0.00073
271.1
75
Significant Digits and Correlation Matrix:
8
-0.361
9
0.310
0.637
9
0.123
0.745
0.921
4
-0.643
0.455
-0.275
-0.144
5
0.956
-0.438
0.304
0.125
-0.830
4
0.738
-0.479
0.352
0.134
-0.830
0.819
6
-0.421
0.403
-0.250
-0.123
0.837
-0.579
-0.841
4
References
(1)
Watson, J. K. G. Vibrational Spectra and Structure; Elsevier: Amsterdam, 1977;
Vol. 6.
(2)
York, 1964.
(3)
Hamilton, W. C. Statistics in Physical Science; The Ronald Press Company: New
Sørensen, G. O. J. Mol. Spectrosc. 1967, 22, 325.
32