Ground State Centrifugal Distortion Constants of Vinyl Isocyanide,
C H o - C H - N C , from the Microwave and Millimeter Wave
Rotational Spectra*
Koichi Yamada and Manfred Winnewisser
Physikalisch-Chemisches Institut der Justus Liebig-Universität Giessen
(Z. Naturforsch. 30 a, 6 7 2 - 6 8 9 [1975] ; received April 9, 1975)
The pure rotational spectrum of vinyl isocyanide in the ground vibrational state has been assigned in the frequency region from 8 GHz to 180 GHz. The measured absorption lines encompass
157 a-type transitions from the I R k , q Q i , 9Q2» q Qs > q(?4 > and qQ5 branches and 48 b-type
transitions from the r P 0 , r P j , r P 2 , r P 3 , r P 4 , r P 5 , r Q 0 , and r Qj branches for values of J up to
54. The rotational constants have been refined and all quartic and sextic centrifugal distortion
constants have been determined using Watson's reduced Hamiltonian. No quadrupole hyperfine
splitting was observed.
I. Introduction
Very recently the transition 2 n — 2 1 2 of vinyl
cyanide has been detected in interstellar space by
Gardner and Winnewisser 1 on the basis of precise
predictions of its rotational spectrum in the microwave and millimeter wave region 2 . From optical and
radioastronomical observations we know at present
that the chemistry which takes place in the cool,
dense, interstellar clouds produces other nitriles such
as the CN-radical, hydrogen cyanide (HC = N ) ,
cyanoacetylene (HC = C — C = N) and methylcyanide (H 3 C —C = N ) 3 . However, there is so far
no experimental evidence that the corresponding
isonitriles can be synthesised under interstellar space
conditions, despite the suspicion that the unidentified
line U (90665) might arise from the HNC molecule 4 , whose laboratory spectrum has yet to be discovered. The presence of vinyl isocyanide (V —NC)
in interstellar space, however, is more probable than
that of smaller isonitriles, since it is relatively stable.
The a-type rotational transitions of this molecule are
very intense because of the large a-component of its
dipole moment (/wa = 3 . 4 7 D and y a b = = 0 . 7 9 D 5 ) , so
that we consider V — NC a good candidate for detection in interstellar clouds.
The rotational constants of vinyl isocyanide for
molecules in the ground state and in the two lowest
excited vibrational states were reported by Bolton,
Owen and Sheridan 5 . They measured several low
/ o-type transitions and four 6-type, Ka = 1 -<— 0,
Reprint requests to Dr. K. Yamada, Physikalisch-Chemisches Institut der Justus-Liebig-Universität
Giessen,
D-6300 Giessen, Goethestrasse 55, West Germany.
transitions in the ground state. They also reported
the vibrational frequencies of 15 fundamentals and
several combination and overtone bands.
The purpose of the present work is to extend the
measurements of the rotational spectrum into the
millimeter wave region in order to refine the rotational constants and to determine the quartic and
sextic distortion constants. A large number of both
a- and 6-type transitions have been identified up to
J = 54 for the ground vibrational state. The observed
frequencies have been analysed by the centrifugal
distortion treatment using J6 terms in the Hamiltonian.
Precise predictions of line frequencies have been
made for radioastronomically interesting transitions
of this molecule on the basis of the adjusted molecular parameters derived from the experimental data
reported here.
The notation used in this paper is the same as
that used by Watson 6 and by Kivelson and Wilson 7 .
II. Experimental P r o c e d u r e s
The sample of vinyl isocyanide was prepared
following the method reported by Matteson and
Bailey 8 . In the first step, N-formylethanolamine was
prepared by the dropwise addition of ethyl formate
to ethanolamine. The product was distilled at about
1 3 0 ° under a vacuum of less than 1 torr. In the next
step, 2-isocyanoethyl benzenesulfonate was obtained
by the dropwise addition of benzenesulfonyl chloride
* This work was started while both authors were at the
Institut für Physikalische Chemie der Universität Kiel,
and has been supported by funds from the Deutsche Forschungsgemeinschaft.
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K. Yamada and M. Winnewisser • Centrifugal Distortion Constants of Vinyl Isocyanide
to N-formyl-ethanolamine in pyridine under a nitrogen atmosphere. The product was extracted with
methylene chloride and concentrated under vacuum.
H 0 C H o C H
+
EtOCHO
o
N H
673
Finally vinyl isocyanide was obtained by adding
potassium hydroxide in ethanol to the ethanol solution of crude 2-isocyanoethyl benzenesulfonate.
2
- > HOCH.,CH 2 NHCHO
+
C6H5S02C1
The product was purified by a fractionation at about
— 5 0 ° C. Finally V — NC was sublimed at dry ice
temperature into the cells of the spectrometers. No
obvious impurity has been found in the spectrum
other than the solvent methylene chloride.
Microwave measurements were carried out in the
frequency region 8 — 1 8 GHz, using a HewlettPackard MODEL 8460 A Microwave Rotational
Resonance ( M R R ) spectrometer employing a 6 foot
X-band Stark cell and 33.333 kHz square wave modulation of the electric field. The reproducibility of
the measurements in the present study obtained by
averaging the center frequencies of the forward and
reverse sweeps through the absorption line profile is
believed to be better than + 20 kHz.
In the spectral region of 7 0 — 1 8 0 GHz, a millimeter wave spectrometer was used with a three meter
free space absorption cell. The use of an on-line
P D P 8/1 minicomputer f o r signal averaging and
data processing with the spectrometer has been
described previously 9 . The accuracy of the measurements with this spectrometer is believed to be
better than + 1 0 kHz, except f o r very weak lines or
overlapping lines 10 .
The spectra were observed and measured at room
temperature. All measurements were made at sample
pressures less than 1 0 - 2 torr.
C6H5S020CH2CH2NC
CH 2 CH - NC
assignment of the millimeter wave spectrum, since
the band-heads form characteristic groups of lines
which are spaced by (B + C ) . The band-head structure of vinyl isocyanide, vinyl cyanide 2 , propynal 1 1
and acrolein 12 are compared in Figure 4. The pattern of the transitions f r o m vinyl isocyanide is quite
similar to that of vinyl cyanide.
The other band-head at Ka = 2 is caused by the
inertial asymmetry of the molecule. It is easily seen
that the inertial asymmetry of propynal is less than
that of the other molecules in Figure 4. Since the
inertial
asymmetry of
vinyl
isocyanide
x =
- 0 . 9 7 7 7 8 6 or bp = - 5 . 5 8 4 5 7 x 1 0 ~ 5 is fairly
large, the K-type doublet of Ka = 4 could be resolved f o r J ^ 10.
The a-type Q branch transitions, which are transitions between the K-type doublets for Ka = 1, 2, 3, 4
' ]
50-t
!
/
III. Spectra and Assignment
A general view of the rotational spectrum arising
f r o m a-type transitions is shown in the Fortrat diagram of Fig. 1 and the spectrum produced by the
6-ytpe transitions is shown in Figure 2. The solid
circles represent observed lines and the open circles
represent predicted line positions. The a-type R
branch transitions, corresponding to AJ =1
and
AKa = 0 transitions, are indicated by showing only
the Ka = 1 lines. The actual pattern of each such
group of transitions is illustrated by a plot of the
transition 7 = 1 4 - * — 1 3 in Figure 3. The band-head
at Kn = 5 is caused by the superposition of centrifugal distortion contributions from terms with Aj
and AJK . This type of band-head is typical for
slightly asymmetric-top molecules and helps in the
Fig. 1. Fortrat-diagram for a-type transitions of V-NC. The
solid and open circles indicate measured and predicted line
positions, respectively. For the a-type R branch only the
ATa = l transitions are indicated
— 0 for 7 = 1 -«— 0). The
inset shows the full £ a -pattern for one transition.
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674
K. Yamada and M. Winnewisser • Centrifugal Distortion Constants of Vinyl Isocyanide 674
The assignment of the lines was achieved by a
bootstrap procedure. Initially the spectrum was
predicted using the previously reported rotational
constants 5 and the centrifugal distortion constants
of vinyl cyanide 2 . The a-type R branch transitions
were identified in the millimeter wave region by
their characteristic band-head structures mentioned
above. The band heads were predicted adequately
with the assumed constants. Refined molecular constants were used to predict further transition frequencies. The absorption lines in the 8 —18 GHz
region belonging to a-type and to 6-type transitions
could then be identified. Assignments in the 8 — 18
GHz region were confirmed by the Stark patterns.
Relative intensity also helped the assignment; otherwise the frequency fit was the chief criterion f o r the
assignment. Further 6-type transitions were then
assigned in the mm-wave region.
In this way
q Qt
157 a-type transitions from
transitions f r o m the
Fig. 2. Fortrat-diagram for the 6-type transitions of V-NC.
The solid and open circles indicate measured and predicted
line positions, respectively.
rQ0
qRx
,
» q Q 2 , q Qs , q Q 4 , and ^Qg branches and 48 6-type
rP0,
rP1
r
l ,> P<>,
rP,,
3 '
rP
4 >
5>
, and r Q 1 branches for values of J up to 5 4 have
been identified including the previously
reported
lines. Some of the lines reported earlier were re-
and 5, supply information concerning high J states
measured in the present study. Because of the fairly
and therefore are important in determining several
small 6-component of the dipole moment the line
intensity of 6-type transitions is much weaker than
of the distortion constants.
The 6-type transitions shown in Fig. 2 also ex-
that of a-type transitions. However, the weak 6-type
hibit band-head structure, which is caused primarily
transitions in the millimeter wave region were mea-
by the inertial asymmetry contribution. Fortunately
sured accurately with the aid of the signal averaging
one component of the 6-type P branch transitions,
system described in Reference
7-1
smoothed line profile of a 6-type transition is il-
and KA = 2<—\,
forms a band-head in
the frequency range of our M R R spectrometer. These
-v-j^—\y-
J = U-*—13
1
The averaged and
lustrated in Figure 5.
band-head lines contributed significantly to the determination of the AK centrifugal distortion constant.
10 .
It should be mentioned that it is impractical to
attempt to measure all 6-type or a-type transition in
1 V"
"V
' f—
K.1
0 CENTER 2
M M
—Lv-'-V-'-V-'—\
139500.5 K 1 7 0 2 . 0
H32M.5
1
K3600
ii7
1—u—^
r"
1—'— — 1 — i
8
1—L
ii
12
1
13 ;
L\—!
1U000
MHz
I U I 73
146537
Fig. 3. Oscilloscope display of the a-type 7=14-<—13 transition of vinyl isocyanide showing the band-head structure. Deviation from rigid rotor frequencies due to centrifugal distortion is indicated by arrows. The weak lines at the tail of
the series are believed to arise from molecules in excited vibrational states.
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K. Yamada and M. Winnewisser • Centrifugal Distortion Constants of Vinyl Isocyanide
K=1
675
K=2
Fig. 4. The band-head structure in the spectrum of several slightly asymmetric (near prolate) top molecules are illustrated
for the a-type 7 = 11 - « - 1 0 transition. Deviation from the rigid rotor pattern due to centrifugal distortion is indicated by
arrows.
the frequency region 0 — 200 GHz which can be expected to have reasonable intensity. Our approach
has been to measure transitions of various branches
belonging to as many K subbands as possible. These
transitions yielded reliable spectroscopic parameters
which may be used to predict the remainder of the
spectrum,
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676
K. Yamada and M. Winnewisser • Centrifugal Distortion Constants of Vinyl Isocyanide 676
H2C2HNC
152!3—-151k ( 2000 SWEEP AVERAGE)
1119000,1188 MHz
1110997.7168 KHz
1118999.0645MHz
Fig. 5. Oscilloscope display of the b-type 152,13
15i,i4
transition of V-NC after 2000 sweeps and 25 point parabolic
smoothing.
IV. Hamiltonian and Analysis
The observed rotational transitions have been
analysed by the use of the reduced Hamiltonian reported by Watson 6 , in which RG = 0,
K = i(X + Y)P + {Z-l(X
-AJ(P)*-AjkPJ?
+
-
Y)}Jz2
AKJ*
+ Hj {P)3 + Hjk (/2)2 J* + HKJ P J* + Hk //
+ (Jx2-Jy2)tt(X-Y)
+ hj(P)2
+
+ hj
+ hJKPJ*
-ÖJP-ÖKJ*2
(1)
measure only two other transitions which belong to
the r P 0 branch. For the other branches we were able
to measure enough transitions. Several lines were
rejected from the fit, indicating an error in measurement, and several high K a lines were omitted
from the fit because higher order centrifugal distortion effects appear to contribute to those line frequencies. Accidentally overlapped or partially resolved A^-type doublets are also omitted. The K-type
doublets in the a-type R branch transitions are
considered to be a single line when the calculated
splitting is less than 5 kHz. Thus 173 lines out of
205 measured transitions have been used for the
least-squares analysis and the standard deviation of
the fit was obtained to be 19.5 kHz, which corresponds to the assumed reproducibility of the frequency measurements.
The constants obtained in the Ir axis representation 13 are listed in Table II. The rotational and
quartic centrifugal distortion constants are well
determined. For the sextic centrifugal distortion
constants, the standard errors are on the order of
\0% of the values of the constants.
+hKJz4}
V. Discussion
{l(X-Y)-djP-öKJ*
(72)2
+ hJK P J * + hK //} (// -
V )
where J, Jx, Jy, and Jz are the operators for the
total angular momentum and its components. The
constants, X, Y, and Z, are the Watson's reduced
rotational constants B, C, and A, respectively, in the
I r axis representation 13 .
The direct diagonalization of the energy matrix
has been used to obtain the rotational energy levels
with the aid of the QR algorithm 14 which diagonalizes tridiagonal matrices rapidly. The computations
were carried out using Fortran IV coded programs
and employing double precision arithmetic utilizing
25 decimal digits throughout the energy calculation.
The iterative least-squares method has been applied
in order to obtain the 15 molecular constants which
appear in the above Hamiltonian.
Table I lists the observed and calculated frequencies for 157 a-type transitions and 48 6-type transitions together with astrophysically important line
frequency predictions. Two 6-type transitions,
ln^— 2q.2 and 6 1 6 - ^ - 7 0 7 , reported in Ref. 5 have
been included in the least-squares fit although the
other lines reported in Ref. 5 were rejected from the
fit. We included these two lines because we could
a) Molecular
Parameters
The determinable parameters found by Watson 6
which are invariant to a unitary transformation of
the Hamiltonian, 2 1 , S 3 , ( J , x aaaa, x'bbbb, x cccc,
x1,
and t 2 , are listed in Table III. Following the planarity condition derived by Watson 6 , the quantity
known as r-defect,
Ax cccc ~
cccc ~
T
QJ-
(
T
2
—
(
2
)
should be zero for the equilibrium structure of a
planar molecule. For the ground vibrational state of
the V — NC molecule the r-defect obtained from
Eq. (2) is 133 kHz, caused by vibrational effects.
Introducing the planarity conditions among the t's,
=
T
Tftftrc =
1 A9 D'
T"ctaa
.1 0 2 ^ 2 !
X"nnn
C j"
Ai
,
+
7bbbb
,
Tcccc
Tbbbh
.
xcccc
Tbbbb
,
ß4
(^V
I
1
/o\
(
'
W
and
Tccaa
1 «
= 2 A~
j
I
^aana
ßl
^cccc
C4
I
j
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/r\
T A B L E I.
OBSERVED AND CALCULATED FREQUENCIES OF VINYL ISOCYANIDE
OBSERVED
CALCULATED
UPPER
LOWER
FREQUENCY
(STANDARD
STATE
STATE
(WEIGHT)
TRANSITION
FREQUENCY
D"?S . - C A L C .
DEVIATION)
IN
MHz
(CONT INUE 0)
ENERGY
LEVFLS
IN
CM-
UPPEP
LOWER
STATE
ST A T E
7 (
5
3)
6 (
5,
2)
7 (
6
1)
-
6 (
6,
o>
7 (
6
2)
-
6 (
6,
1)
8 (
0
8)
-
7 (
0.
7)
81678. 4555 (
0.0334)
12.285
9. 560
ft (
1
7)
-
7 (
1»
6)
84021.1049(
0.0034)
14.165
11. 362
8 (
1
8)
-
7 (
1,
7)
79Ö88.2568(
0.0034)
13.544
10. 879
8 (
2
6)
-
7 {
2,
5)
8 2 3 5 4 . 3907 (
0.0032)
18
.525
15. 773
8 (
2
7)
-
7 (
2,
6)
81993.2379(
0.0032)
18
.494
15. 759
8 (
3
5)
-
7 (
3,
4)
82108. 9387 (
0.0029)
26.228
23. 489
8 (
3
6)
-
7 (
3,
5)
82103.2358(
0.0329)
26.227
8 (
4
4)
-
7 (
3)
82095.6931(
0.0026)
37.030
23. 489
34. 292
7 (
4,
5,
7 <
5,
7 (
ft»
8 f
4
5)
ft (
5
3)
-
8 (
5
8 (
6
2)
-
7 (
7 1 8 3 6 . 0 8 5 4 ( 1 . 0 )
7 1 8 4 8 . 2 2 0 1 ( 1 . 0 )
71836.0846(
0.0324)
7 1 3 4 8 . 2 3 7 6 (
0 . 0 J 26)
7 1 8 4 8 . 2 3 7 5 (
0.012ft)
0 . 0008
-0 .0175
43.166
45. 770
65.099
62. 702
65.099
62. 702
4)
82095. 6607 (
0.0026)
37.030
34. 292
2)
82100.8123 (
0.0325)
48. 166
3)
82100 . 8122 (
0.0025)
5 0 . 9 0 4
5 0 . 9 0 4
1)
82113.5633 (
0.0028)
57.338
6 5 . G 99
65. 099
8 (
6
3)
-
7 (
6»
2)
82113.5633(
0.0328)
5 7.338
8 (
7
1)
-
7 (
7,
0)
82131 . 5200 (
0.0035)
87
8 (
7
2)
-
7 (
7,
1)
82131. 5200 (
0.0035)
87.815
9 (
0
9)
-
0,
9 (
1
3)
-
8)
7)
9 (
1
8 (
1.
8)
2
9)
7)
-
9 (
-
8 (
2 •
8 (
« (
1,
.815
48. 166
85. 075
« 5 . C 75
9 1 7 7 9 . 3 7 5 4 ( 1 . 0 )
91779.3717 (
0.0035)
0 . 00 37
15.346
12. 285
9 4 4 9 2 . 3 1 8 3 ( 1 . 0)
8 9 8 4 7 . 5 6 1 1 ( 1 . 0 )
9 4 4 9 2 . 2 9 8 1 (
0.0335)
0 .
17.317
14. 165
89847. 5442 (
0.0035)
0 .0169
16.541
13. 544
92736 . 1904 (1.
92736.1823(
0.0333)
0 .
21.618
18. 525
0076
9(
2
8»
-
8 (
2,
6)
7)
9 2 2 2 2 . 5 6 0 3 ( 1 . C )
92222.5503(
0.0333)
0 .0095
21.571
18. 494
9 (
3
ft)
-
8 (
3,
5)
9 2 3 8 6 . 9 0 8 5 ( 1 . 0 )
9 2 3 8 6 . 8 9 7 4 (
0.0030)
0 .0111
29.309
26. 223
9(
1
7)
-
8 (
3,
ft)
9 2 3 7 6 . 4 6 6 3 ( I . D )
9 2 3 7 6 . 4 5 2 7 (
0.0029)
0 .0135
29.309
26. 227
9 (
4
5)
-
8 (
I»,
9 2 3 6 3 . 4 8 9 3 ( 1 . 0 )
92363.5363(
0.0027)
-0 . 0470
40.111
37. 030
9 (
4
r
6)
-
8 (
9 2 3 6 3 . 4 8 9 3 ( 1 . Ü )
9 2 3 6 3 . 4 5 8 5 (
0.0027)
0 . 0308
40.111
3 7 . 0 30
-
8 (
9 2 3 6 6 . 5 1 0 2 (
0.0326)
5 3 . 9 8 6
50. 904
9 (
5
5)
-
8 (
9 2 3 6 6 . 5 0 9 9 (
0.0326)
9 (
6
-
ft (
9 2 3 7 9 . 4 0 4 4 (
0.0029)
9 (
ft
3)
i• )
-
8 (
6»
3)
9 (
7
-
8 (
7,
1)
9 (
7
2)
3)
-
8 (
7,
2)
9 (
>
5)
5,
3)
)
5,
4)
j
6»
2)
9 2 3 6 6 . 5009
0)
0202
(1.0)
9 2 3 7 9 . 4039 (1.
0)
9 2 3 9 8 . 7 3 7 6 ( 1 . 0 )
9 2 3 7 9 . 4 0 4 4 (
0.0029)
9 2 3 9 3 . 7 4 5 3 (
0.0036)
92398.7453(
0.003ft)
92423.1909(
0.0346)
92423.1909(
0.0046)
-0 .0090
-0 . 0005
5 3 . 9 8 6
50. 904
7G
67. 333
.919
7 0 . 9 1 9
6 7. 8 3 8
90.ft 97
-0 . 0077
90.897
87. 815
87. 815
1 1 3 . 9 0 1
110. 818
0 . 0G 6 5
1 1 3 . 9 0 1
1 1 0 . 8 18
9 (
8
1)
-
8 (
8,
0)
9 (
8
2)
-
8 (
8»
1)
10 (
0
10)
_
9 (
0,
9)
1 0 1 8 4 3 . 8 2 9 9 ( 1 . C )
101343.8659(
0.0036)
-0 .0360
18.743
10 (
1
9)
-
9 (
1,
8)
1 0 4 9 5 1 . 7 2 2 5 ( 1 . 0 )
104951.7539(
0.0035)
-0 .
0314
20.817
15. 346
17. 317
10 (
1
10)
-
9 (
1»
9)
9 9 7 9 8 . 0 2 6 2 (
0.0035)
1 9 . 8 6 9
16. 541
10 (
2
8)
-
9 (
2,
7)
1 0 3 1 4 6 . 3 1 3 3 ( 1 . 0 )
103146.8409(
0.0033)
- 0 .
0276
25.059
21. 613
10 (
2
9)
-
9 (
2,
8)
1 0 2 4 4 4 . 8 6 9 4 ( 1 . 0 )
1 0 2 4 4 4 . 3 3 7 0 (
0.0033)
-0 .
0176
24.98«
21. 571
10 (
3
7)
-
9 (
3,
ft)
10 2 f t 7 0 . 5 6 0 2 ( 1 . 0)
102670.5671(
0.0330)
-0 .
0069
32.734
29. 3 C 9
9 2 4 2 3 . 1 9 7 4 ( 1 . 0)
10 (
3
8)
-
9 (
3,
7)
1 0 2 6 5 2 . 6 9 1 5 ( 1 . 0 )
1 0 2 6 5 2 . 6 3 5 2 (
0.0330)
10(
4
6)
-
9 (
4,
5)
1 0 2 6 3 3 . 3 6 2 8 ( 0 . 0 )
102633.4681(
0.0327)
7)
-
9 (
4,
ft)
5
5)
-
9 (
5,
4)
ft)
-
I
9 (
M
I
4)
-
9 (
10 (
1C2633.3628(0.0)
5)
-
9 (
3)
-
9<
10 (
7
7
ft.
ft.
-
9 (
7,
3)
1
10 (
8
2)
-
9 (
8,
1)
3)
-
9 (
8 ,
2)
I
10 (
10 (
10 (
10 (
10 (
10 (
«5
ft
ft
a
5,
1 0 2 6 3 3 . 3 6 2 3 ( 0 . 0 )
3)
4)
7,
2)
1 0 2 6 4 5 . 8 0 5 4 ( 1 . 0 )
I
1
1 0 2 6 6 6 . 2 4 3 7 ( 1 . 0 )
10 2 6 9 2 . 7 1 3 0
(1. 0 )
0 . 0063
32.733
29. 309
1053
4 3 . 5 3 5
40. 111
0 . 0631
4 3 . 5 3 5
40. 111
5 7 . 4 0 9
53. 936
5 7 . 4 0 9
53. 986
70. 919
-0 .
102633.2997(
0.0327)
102633.2985(
0.0327)
1 0 2 6 3 3 . 2 9 7 « (
0.0327)
102645.8245(
0 . G03 0 )
102645. 8245 (
0.0030)
0.0037)
-0 .0191
10 2 6 6 6 . 2 4 6 5 (
102656. 2465 (
0.0037)
- 0 . 0028
102692.7194(
0.0347)
102692.7194<
0.0047)
0.
0650
74.343
7 4 . 3 4 3
70. 919
94.321
90. 897
90. 397
94.321
117
-0 .0364
.326
1 1 7 .326
REMARKS
113. 901
Unauthenticated
1 1 3 . 90 1
Download Date | 10/2/16 10:01 AM
T A B L E I.
TRANSITION
UPPER
LOWER
STATE
STATE
**
A
1 (
TYPE
R
OBSERVED
AND
CALCULATED
F R E Q U E N C I E S OF
OBSERVEO
CALCULATED
FREQUENCY
(STANDARD
FREQUENCY
VINYL
ISOCYANIDE
3BS.-CALC.
DEVIATION)
(WEIGHT)
I N M H z(CONTINUE0)
ENFPGY
UPPFP
STATE
LEVELS
I N CM-1
LOWER
STATE
0,
-
0 (
0,
0)
10255 . 5 3 1 0 ( 1 . 0 )
1 0 2 5 5 . 5 7 8 9 (
0 .
0006)
0 .
0021
3
.342
0 .
coo
342
2(
0 ,
2)
_
1 (
0,
1)
20506 . 7800
(0.
0)
2 0 5 0 6 . 7 6 4 3 (
0
2 (
1 ,
1)
-
1 (
1,
0)
21029 .0400
(0.
0)
21029. 0305 (
0 .
2 <
1»
2)
-
1 (
1,
1)
19993 . 9 8 0 0 ( 0 . 0 )
1 9 9 9 3 . 9 1 6 2 (
0. 0011)
3 (
0»
3)
_
2 (
3 •
2)
3 0 7 4 9 . 3300 (0 . 0 )
3 0 7 4 9 . 1 6 6 1 (
0 . 0317)
3 (
1,
2)
-
2 (
1,
1)
31540 . 6 9 0 0 ( 0 . 0 )
3 1 5 4 0 . 7 2 1 4 (
0 .
0317)
- 0 .0314
3 . 6 5 0
2. 593
3 (
1,
3)
-
2 (
It
2)
2 9 9 8 8 . 0500
2 9 9 8 3 . Ü 6 3 4 (
0 .
0016)
-0 .0134
3 . 5 4 7
2. 546
3 (
2,
1)
-
2 (
2,
0)
30786 . 4 1 0 0 ( 0 . 0 )
30786. 2321 (
0 .
0016)
0 . 1 7 7 9
3 . 2 3 6
7. 209
3 (
2,
2)
-
2 (
2,
i)
30763 . 9 6 0 0 ( 0 . 0 )
3 0 7 6 8 . 8 9 9 3 (
0. 0016)
8 . 2 3 5
7. 209
3 . 4 1 9
2. 052
5.
3. 650
(0.0)
.
0 311)
0
1 . 0 2 6
0 .
0 312)
-0 .
0405
2 . 5 9 8
1. 8 9 7
0 .
0638
2.54ft
1. 879
.
1361
2 . 0
- J
0
. 0 1 5 7
.
0607
52
1. 026
4 (
0,
4)
_
3 (
0,
3)
40973 .4074 (
0 .
4 (
1,
3)
-
3 (
1,
2)
42048 . 852L (
0 . 00 22 )
4 (
1,
4)
-
3 (
1,
3)
39978. 8702 (
0 .
0021 )
4 . 8 8 0
3. 547
4 (
2,
2)
-
3 (
2,
1)
4 1 0 6 4 . 8 7 1 9
0 .
0320 )
9 . 6 0 6
3. 236
?(
2,
2)
41021. 5581 (
0 .
0 320)
9 . 6 0 4
8. 235
3 (
3,
0)
4 1 0 3 7 . 6 5 1 6 (
0 .
001«)
1 7 . 3 2 8
15. 959
4 1 0 3 7 . 5 1 5 5 (
0
0018)
1 7 . 3 2 8
15. 959
(
0 3 22)
053
4 (
2,
3)
-
4 (
3,
1)
-
4 (
3.
2)
-
3 (
3,
1)
5 (
0,
5)
_
4(
0,
4)
51190. 1460
(
0 .
5 (
1,
4)
-
4 (
1,
3)
5 2 5 5 2 . 2 5 1 1
(
0 . 0 3 2 6)
6 . 8 0 6
5. 0 53
6 . 5 4 7
4. 330
.
5 (
1»
5)
4 (
1,
4)
49965. 2772 (
3 . 0025)
5 <
2,
3)
-
4 (
2 i
2)
5 1 3 5 7 . 6 5 6 9 (
0 .
5 (
2,
4)
-
4 (
2.
3)
5 1 2 7 1 . 0 9 7 7 (
0 . 0324)
2)
-
5 (
3,
4 (
3,
4,
3)
-
4 (
5 (
1)
-
4 (
5(
2)
-
4 (
4,
3,
1)
51300 .«410
(
0
5
0326 )
-
3,
11
0324)
.
0022 )
2)
5 1 3 0 0 . 3 6 4 9 (
0 .
0322)
0)
5 1 3 0 2 . 3 2 3 2 (
0 .
1)
51302. 3224 (
0 .
0020 )
0320 )
.126
.319
9. 604
1 9 . 0 3 9
1 9 . 0 3 9
2 9 . 8 4 2
28. 131
2 9 . 8 4 2
28. 131
0»
6)
_
5 (
0
5)
61330. 1147 (
0 .
0030 )
7
1,
5)
-
5 (
1,
4)
63049. 6522 (
0 .
0330 )
8 . 9 0 9
»
9. 606
17. 328
6 (
8
.174
.546
17. 323
5. 126
6. 806
6. 547
6(
1,
6)
-
5 (
1,
5)
5 9 9 4 6 . 2 7 0 9 (
0
6 (
2,
4)
-
5 (
2,
3)
61668. 0161 (
0 .
0327)
6 (
2,
5)
-
5 (
2,
4)
6 1 5 1 6 . 7 4 0 7 (
0 .
6 (
3,
3)
-
5 (
3,
2)
6 1 5 6 6 . 6 7 2 0
(
6 (
3,
4)
-
5 (
3,
3)
6 1 5 6 5 . 4030 (
0 . 032 5)
2 1 . 0 9 3
19. 039
6 (
4,
2)
-
5 (
4,
1)
6 1 5 6 5 . 3 2 0 3 (
0 .
31
29. 842
6 (
4,
3)
-
5 (
4,
2)
6 1 5 6 5 . 3 1 6 7 (
0. 0323)
3 1 . 8 9 6
29. 842
1)
-
5 (
5,
0)
6 1 5 7 2 . 2 0 6 5 (
0 .
0022 )
4 5 . 7 7 0
43. 716
2)
-
5(
5,
1)
61572. 2065 (
0 . 0022 )
4 5 . 7 7 0
43. 716
7. 174
,
.
0029)
1 3 . 3 7 6
11. 319
0327)
1 3 . 3 6 6
0 . 0325 )
2 1 . 0 9 3
11. 314
19. 039
0023)
.896
6 (
5.
7 (
0 ,
7)
_
6 (
0 ,
ft)
71544 . 1 8 3 5 ( l . j )
7 1 5 4 4 . 1 3 4 8 (
0 .
0132)
.0012
9 . 5 6 0
1 ,
6)
-
6 (
1,
5)
73539 . 7 5 0 9 ( 1 . 0 )
7 3 5 3 9 . 7 3 3 3 (
0 .
0 3 3 2)
0
. 0 1 7 6
1 1 . 3 6 2
8. 9 0 9
11
7)
-
6 (
1»
6)
69920 . 3 9 7 3 ( 1 . 0 )
6 9 9 2 0 . 8 9 4 3 (
0 .
0332)
0
. 00 30
1 0 . 8 7 9
8 .
5)
-
6 (
2,
4)
71999 .2179
(1.0)
7 1 9 9 9 . 2 4 0 0 (
0 .
0330 )
.
0221
1 5 . 7 7 8
(1.0)
.
7(
- 0
7 (
?,
7 (
2,
6)
-
6 (
2,
5)
7 1 7 5 7 .7<*13
71757. 7117 (
0
7 (
3,
4)
-
6 (
3,
3)
71835 . 7 8 8 6 ( 1 . 0 )
7 1 8 3 5 . 7 9 7 4 (
0 . 0027)
7 (
3,
5)
-
6 (
3,
4)
71832 . 9 4 8 0 ( 1 . 0 )
7 1 8 3 2 . 9 4 3 8 (
0 .
0327)
0
7 (
4,
4)
-
6 (
4,
3)
71829 . 6 9 8 3 ( 1 . C )
7 1 8 2 9 . 6 3 7 6
(
0 .
0325)
c . 0 1 1 2
3)
-
6 (
4,
2)
71829 . 6 9 8 8 ( 1 . 0 )
71829. 6994 (
0 .
03 2 5 )
2)
-
6 (
5,
1)
71836 . 0346 (
0
7 (
7 (
7 (
5,
.
.
00 30 )
0 324 )
- 0
0
- 0
- 0
546
13. 376
0301
1 5 . 7 5 9
13. 366
. 00 83
2 3 . 4 8 9
21. 093
.
2 3 . 4 8 9
21. 093
3 4 . 2 9 2
31. 896
.
0042
0006
3 4 . 2 9 2
43
.166
n
3. 419
1 1 . 3 1 4
6 (
ft ( 5
co
BRANCH
1)
5 (
PEMARKS
Unauthenticated
31. 896
Download4 5Date
| 10/2/16 10:01 AM
. 770
n
I.
TABLE
OBSERVED AND CALCULATED FREQUENCIES OF VINYL ISOCYANIDE IN
TRANSITION
OBSERVED
CALCULATED
(STANDARD
UPPER
LOWE P
FREQUENCY
STATE
STATF
(WEIGHT)
FPEQUENCY
DEVIATION)
MHz
(CONT INUE 0)
FNEPGY
STATF
STATE
1 4 3 . 3 3 8
139. 911
143
139. 911
9 (
9
0)
-
9 (
9
L ) ;
0
11)
-
10 (
10)
10>
-
in
0
1
(
1
9)
-
10 (
1
10)
1 0 9 7 3 9 . 1 0 6 3 ( 0 . 0 )
109739. 0644 (
0.G335)
0 .
0419
2 3 . 5 3 0
19.
1C
( 2
8)
1 1 3 5 8 8 . 0 3 8 1 ( 0 . 0 )
1 1 3 5 8 7 . 9 3 9 9 (
0 . 0 0 3 3 )
0 .
0982
23.848
0 .
0222
28.74ft
25.
0.0J33)
0503
3 6 . 5 0 2
0076
36.500
24.
32.
32.
-0 . 0072
0 .0997
4 7 . 3 0 1
43.
11 (
11<
11 (
1
11)
11 (
?
9)
-
11 (
2
10)
-
3
8)
10 (
11 (
-
10 (
LU (
3
)
102724. 4037 (
0.
1 0 2 7 2 4 . 3 9 4 9 ( 1 . 0 )
102724. 4037 (
0 . 0 3 5 8 )
-0 . 0033
1 1 1 8 6 9 . 4 9 0 0 ( 1 . 0 )
1 1 1 8 6 9 . 5 1 5 4 (
0.033ft)
-0 . 0254
115
115397. 8119 (
0 . 0 0 3 5 )
3 9 7 . 8 4 ( 1 . 0 )
2
9)
1 1 2 6 5 9 . 5 1 2 3 ( 1 . 0 )
3
7)
1 1 2 9 6 0 . 9 9 4 0 ( 1 . 0 )
1 1 2 6 5 9 . 4 9 0 1 (
1 1 2 9 6 0 . 9 4 3 7 (
8)
1 1 2 9 3 1 . 9 4 1 5 ( 1 . 0 )
1 1 2 9 3 1 . « 3 3 9 <
CJ58)
0.C329)
11 (
3
9)
-
11 (
4
7)
-
10 (
4
6)
1 1 2 9 0 5 . 7 2 6 3 ( 0 . 0 )
1 1 2 9 0 5 . 7 3 3 5 (
0 . 0 329)
0.0327)
11 (
4
8)
-
10 (
4
7)
1 1 2 9 0 5 . 4 9 6 6 ( 0 . 0 )
112905. 3969 (
0 . 0 3 2 7 )
11 (
^
ft)
-
10
112901. 2974 (
11 (
5
7)
-
10 (
11 (
6
F,
5)
-
6)
10
-
10 (
6
I K
7
4)
11 (
7
11 (
8
11 (
8
I K
9
5)
3)
4)
2)
11 (
9
11(10
11(10
( 5
5
( 6
5) T
6) f
1 1 2 9 0 1 . 3 1 8 2 ( 1 . 0 )
4)
)
5)
/
)
-
10 (
7
3)
-
1U (
7
<•> f
-
10 (
8
2)
3)
I
1 1
2)
1
/
)
1 1 2 9 3 4 . 0 4 5 9 ( 1 . 0 )
\
-
10 (
8
-
10 (
9
3)
-
10 (
9
1)
-
10 (10
0)
-
10 (10
1) /
2)
1 1 2 9 1 2 . 8 5 9 7 ( 1 . 0 )
112962.3771(1.0)
1 1 2 9 Q 6 . 6 4 7 8 ( 1 . 0 )
1 1 2 9 0 1 . 29*55 (
0 . 0 3 2 7 )
0 . 0 0 2 7 )
1 1 2 9 1 2 . 8 3 7 0 (
0 . 0 3 3 0 )
1 1 2 9 1 2 . 8370 (
0 . 0 3 3 0 )
112934. 0535 (
0 . 0 3 3 7 )
1 1 2 9 3 4 . 0 5 3 6 (
0 . 0 3 3 7 )
1 1 2 9 6 2 . 3 3 6 3 (
0 . 0 0 4 6 )
1 1 2 9 6 2 . 3 3 6 3 (
0 . 0 3 4 6 )
112996. 6151 (
0 . 0 0 5 7 )
1 1 2 9 9 6 . 6 1 5 1 (
0 . 0 3 5 7 )
113036. 3240 (
0 . 0 0 7 0 )
1 1 3 0 3 6 . 2 8 7 0 ( 0 . 0 )
113036. 3240 (
0 . 0 3 7 0 )
0 .
0.
0.
0336
.338
18.
20. 817
.667
4 7 . 3 0 1
6 1 . 1 7 5
733
5 35
43. 53 ^
S 7. 4 0 9
57. 4 0 9
6 1 . 1 7 5
7 8 . 1 0 9
74. 343
-0 .
0273
7 8 . 1 0 9
74. 343
-J .
0077
9 8 . 0 8 8
1 2 1 . 0 9 4
0 .
0403
94.
94.
321
321
117. 326
1 2 1 . 0 9 4
117. 326
1 4 7 . 1 0 7
143. 338
1 4 7 . 1 0 7
143.
0.
0327
1 7 6 . 1 0 4
172. 3 33
-0 .
0370
1 7 6 . 1 0 4
172.
333
333
3 2 . 9 8 6
22. 4 7 5
24. 6 6 7
2 3 . 5 30
23. 8 4 3
3 2 . 8 4 4
28. 746
0
12)
-
11 (
0
11)
1 2 1 8 5 4 . 7 0 4 2 ( 1 . 0 )
1 2 1 3 5 4 . 7 0 0 3 (
0 . 0 3 3 5 )
3 . 00 39
2 6 . 5 3 9
1
11)
-
11 (
1
10)
1 2 5 8 2 3 . 7 0 0 8 ( 1 . 0 )
125828. 7003 (
0 . 0 3 3 5 )
3 . 00 35
2 8 . 8 6 4
1
11)
1 1 9 6 7 0 . 1 1 8 0 ( 1 . 0 )
1 1 9 6 7 0 . 1 1 7 9 (
0 . 0 0 3 4 )
124060.24
1 2 4 0 6 0 . 2 4 4 9 (
0 . 0 3 3 2 )
10)
1 2 2 8 6 5 . 5 9 8 5 ( 1 . 0 )
1 2 2 8 6 5 . 6 1 2 3 (
0 . 0 3 3 2 )
0. 0 0 0 1
0 . 00 0 5
-0 . 0 1 4 3
3
8)
1 2 3 2 5 9 . 1 2 6 9 ( 1 . 0 )
1 2 3 2 5 9 . 1 3 5 9 (
0 . 0 0 2 9 )
-0 .
0090
4 0 . 6 1 3
36. 502
11 (
3
9)
1 2 3 2 1 4 . 1 1 6 5 ( 1 . 0 )
1 2 3 2 1 4 . 1 0 3 5 (
0 . 0 3 2 9 )
0 .
0130
40
36.
11 (
4
7)
1 2 3 1 8 0 . 6 2 1 9 ( 0 . 0 )
123180 . 5353 (
0 . 0 3 2 6 )
0361
51.410
47. 301
8)
1 2 3 1 7 9 . 9 3 2 3 ( 1 . 0 )
47. 301
12 (
1
12)
-
11 (
12 (
2
10)
-
11
12 (
2
11)
-
11
12 (
3
9)
-
11 (
12 (
3
10)
-
1 2 (
4
8)
-
11 (
( 2
( 2
4
9)
-
12 (
5
7)
-
11
12 (
5
8)
-
12 (
6
6)
11 (
-
11
7)
-
11
11 (
7
983
734
0227
12 (
12 (
869
059
0 .
98.088
I•
( 5
5
( ft
( ft
9)
123179. 9554 (
1 2 3 1 7 0 . 6 2 6 3 (
0 . 0 0 2 6 )
0231
51
0 . 0 3 2 6 )
0 .
0075
6 5 . 2 8 3
7)
1 2 3 1 7 0 . 6 3 4 3 ( 1 . 0 )
123170 .6224 (
0 . 0 3 2 6 )
0.
0119
6 5 . 2 8 3
61.
123130 . 6551 (
0 . 0 3 3 0 )
32.218
73. 109
6)
)
1 2 3 1 8 0 . 6 2 1 9 ( 0 . 0 )
123130 . 6551 (
0 . 0 3 3 0 )
4)
\
1 2 3 2 0 2 . 1 9 6 2 (
0 . 0 3 3 7 )
I
1 2 3 2 0 2 . 1 9 6 2 (
0 . 0 3 3 7 )
123232. 0512 (
0 . 0 0 4 5 )
123232. 0512 (
0 . 0045)
1 2 3 2 6 3 . 7 5 9 3 (
0 . 0 0 5 4 )
1 2 3 2 6 8 . 7 5 9 8 (
0 . 0 3 5 4 )
1 2 3 3 1 1 . 5 8 4 4 (
0 . 0 3 6 5 )
1 2 3 3 1 1 . 5 8 4 4 (
0 . 0 0 6 5 )
5) )
12 (
6)
-
11 (
7
12 (
8
4)
-
8
12 (
5)
11 (
3
-
11
12 (
9
3)
-
11 (
9
2)
12 (
9
4)
-
11 (
9
3);
12(10
2)
_
11 (10
1)
12(10
3)
-
11 (10
2)
12(11
1)
-
11 (11
0)
12(11
2)
1) f
11 (11
12
5)
3)
1 2 3 2 0 2 . 1 9 1 6 ( 1 . 0 )
)
<•> /
1 2 3 2 3 2 . 0 5 0 8 ( 1 . 0 )
)
123268. 7199 (1.
0)
\
f
\
1 2 3 3 1 1 . 5 8 5 6 ( 1 . 0 )
123360 . 8568 ( 0.
0)
1233ft0.1277(
0 . 0 0 8 0 )
123360. 1277 (
0 . 0 3 8 0 )
-0
.
0332
.409
32.213
-0 .
-0 .
0046
0004
-0 . 0399
0.
0.
0012
73. 109
1 0 2 . 1 9 8
121. 094
1 2 5 . 2 0 5
121. 094
1 5 1 . 2 1 9
147. 107
1 5 1 . 2 1 9
147. 1 C 7
1 8 0 . 2 1 7
17FT. 1 0 4
130
.217
176. 104
2 1 2 . 1 7 5
2 C 8. 060
203. 0 6 0
26. 539
13(
0
13)
12)
131798. 7428 (
0 . 0 0 3 5 )
3 0 . 9 3 6
13 (
1
12)
-
12 (
L
11)
136242. 5281 (
0 . 0 3 3 5 )
33
13 (
1
13)
-
12 (
L
12)
3 1 . 8 4 4
13 (
2
11)
(
2
10)
129*590 . 7474 (
134563.5696(
G.0034)
-
0.0332)
37.474
12
175
1 2 5 . 2 0 5
2 1 2 . 1 7 5
7291
61. 175
9 8 . 083
9 3 . 088
1 0 2 . 1 9 8
_
r o
500
1 2 3 1 7 0 . 6 3 4 3 ( 1 . 0 )
-
-
.610
6)
5)
( 8
2 7 . 5 2 2
0.
-0 .
7
7
5 4 ( 1 . 0 )
.408
PEMAR KS
743
2 2 . 4 7 ^
24
12 (
ft
CM-
LOWER
1)
9
12 (
IN
UPPEP
2)
10 (
10 (
12 (
LEVFLS
_
9
11(
DBS . - C A L C .
28. 864
522 Unauthenticated
2. 986
Download 3Date
| 10/2/16 10:01 AM
27.
n
K. Yamada and M. Winnewisser • Centrifugal Distortion Constants of Vinyl Isocyanide 680
680
in
v
rv
<t
T
UJ
Or
ra
rara
o cr rr pr or cc 00 CC in in rr a
J- rr
TH
-3 rH rH rH CD or
cr cr CJ CD tH r-l
oo iß iß -3 -3 CM CM CM CM
t-l CM P.) <M CM
p^
m in in in
r-l r-l r^ N- vC lC
CM CM r-l T-H CD
CD cr cr
Pr
lO or -3 -3 rr cr Pr rH rH in in CD
Pr ro .3 P^ X
>D
r— in in in in
lO rr rr
P^
CO a r^ ^ \T vO vT) vT vT vT iT in
cn -3 on -3 CM
M tn INJ CM CM CM in in r-l r-l
CM CD CD rH
-3 -3 LA in »ß iß CO 0C O CD CM CM in in
T-L
•H T-L
CD CD CM CM
P»
oo or rH rH -3 -3
r-l CV CM CM CM
cr vD (JO vD in cr cr in in
CD pr rH P-- K in in in m
CM CM in in
00 CD
PO pr PO pr rr -3 J- if m. v£> vO
rH
T-H rH
in in CJ o CD CD <c 00 f»3 K
CT rr rH
oo <£> iß iß lT rr pr K r^ in in in IT P-.
CM A CD CO oc R - T^ lO vD
vD
vT lO <£>
fO ro PO pr in in
p^ p^ PT pr CM CM
lO lC vO iD in in
in in in in CT
iß vD •o vD
m
Pr, .3 .3 in in iß lO ao OO CD CL. CM CM in in
r-l •r-l
-H
T-1
J- J- vD lC T-L rH
or OO r-l rH in in
rH r-l CM CM CM CM
PO
\D
cr cr in
CT
R^
CM CD
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TRANSITION
UPPFR
LOWER
STATF
STATE
15 (
2
13)
15 (
2
14)
15 (
3
15 (
3
15 (
15 (
OBSERVED
AND
CALCULATED
FREQUENCIES
OBSERVED
CALCULATED
FREQUENCY
(STANDARD
OF
FREQUENCY
ISOCYANIHE
DBS.-CALC.
DEVIATION)
(WEIGHT)
IN
(CONT INUED)
MHz
ENFPGY
LFVFLS
IN
CM-1
UPPER
LOWER
STATE
STATE
4 7 . 5 0 6
42.
4 7 . 1 7 9
4 2 . 0 6 1
0 . 0 1 4 4
5 5 . 0 1 2
49.
•0 . 0 0 4 5
5 4 . 9 9 8
4 9 . 8 5 9
5 5 . 7 9 3
6 0 . 6 5 6
6 5 . 7 9 3
6 0 . 6 5 6
0 . 0 0 3 5 )
1 5 3 4 2 5 . 8 1 1 3 (
U.0334)
11)
154213 . 5532
(1 . 3 )
1 5 4 2 1 3 . 5 3 8 3 (
0 . 0 3 3 1 )
12)
1 5 4 0 7 5 . 6701
(1. 0)
1 5 4 0 7 5 . 6 7 4 6 (
0 . 0 0 3 1 )
4
10)
1 5 4 0 2 3 . 3 8 7 2 ( 1 . 0)
1 5 4 0 2 3 . 3 8 9 4 (
0 . 0 3 2 9 )
•0.0022
4
11)
154020 . 2 7 8 9 ( 1 .0)
1 5 4 0 2 0 . 2 3 6 1 (
0 . 0 0 2 9 )
•0.0 0 72
9)
153987 .7642
(1 . 0 )
1 5 3 9 3 7 . 7 9 9 5 (
0 . 0 3 3 1 )
•0 .
7 9 . 6 6 5
7 4 . 5 2 8
5
10)
153937 .7642
(1 .
1 5 3 9 8 7 . 7 6 4 1 (
0 . 0 3 31)
14 (
6
8)
1 5 3 9 8 8 . 8 1 9 « (
0 . 0 3 3 5 )
14 (
6
9)
1 5 3 9 3 8 . 8 1 9 5 (
0.0035)
14 (
7
7)
1 5 4 0 0 8 . 9 3 2 1 (
0 . 0 0 4 1 )
14 (
7
8)
1 5 4 0 0 8 . 9 3 2 1 (
0 . 0 0 4 1 )
8
6)
1 5 4 0 4 1 . 8 5 7 5 (
0 . 0 3 4 6 )
2
12)
14 (
2
13)
12)
-
14 (
3
13)
-
14 (
3
4
11)
-
14 (
4
12)
-
14 (
15 (
5
10)
-
14 (
5
15 (
5
11)
-
14 (
15 (
6
9)
-
15 (
6
10)
-
15 (
7
8)
-
15 (
7
9)
-
15 (
8
7)
-
14 (
1 5 3 9 8 8 . 3 4 1 1 ( 1 . 0)
154003 .9169
15 (
8
8)
-
14 (
8
7)
15 (
9
6)
-
14 (
9
5)
15 (
9
7)
-
14 (
9
6 ) /
15(10
5)
_
14
15
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6)
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5)
15
(11
4)
-
14(11
3)
15
(11
5)
-
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14
4)
f
15(12
3)
-
14(12
2)
15
4)
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14(12
3)
15(13
2)
-
14(13
1)
(13
3)
-
L
15
14(13
2)
1
15
(14
1)
-
14(14
0)
15
(14
2)
-
14(14
1)
16
0
16)
_
15 (
0
16 (
1
15)
-
15 (
1
(10
(11
0)
(1. 0 )
1 5 4 0 4 1 . 3 6 6 2 ( 1 . 0)
154034 . 7 5 1 6 ( 1 .0)
L
1 5 4 0 4 1 . 8 5 7 5
(
0 . 0 0 4 6 )
1 5 4 0 3 4 . 7 2 8 3 (
0 . 0 3 4 9 )
1 5 4 0 3 4 . 7 2 8 3 (
0 . 0 3 4 9 )
•0.
0174
0353
0.0001
0.0216
•0.0152
7 4 . 5 2 8
96.600
91.
96.600
9 1 . 4 6 4
1 1 6 . 5 8 2
1 1 1 . 4 4 5
.582
1 3 9 . 5 9 2
0 . 0 0 8 7
0 . 0 2 3 3
863
7 9 . 6 6 5
116
464
1 1 1 . 4 4 5
1 3 4 . 4 5 4
1 3 9 . 5 9 2
1 3 4 . 4 5 4
1 6 5 . 6 1 0
160.470
1 6 5 . 6 1 0
160.470
1 9 4 . 6 1 3
1 8 9 . 4 7 2
1 9 4 . 6 1 3
1 8 9 . 4 7 2
1 5 4 1 3 6 . 0 3 6 4 (
0 . 0 0 4 9 )
154136. 0864 (
0 . 0 0 4 9 )
1 5 4 1 9 5 . 1 3 5 7 (
0 . 0 0 5 3 )
1 5 4 1 9 5 . 1 3 5 7 (
0 . 0
1 5 4 2 6 1 . 4 2 1 9 «
0 . 0 0 7 0 )
1 5 4 2 6 1 . 4 2 1 9 (
0 . 0 3 7 0 )
1 5 4 3 3 4 . 6 7 9 7 (
0 . 0 1 1 1 )
1 5 4 3 3 4 . 6 7 9 7 (
0 . 0 1 1 1 )
1 5 4 4 1 4 . 7 5 6 4 (
0 . 0 1 7 4 )
1 5 4 4 1 4 . 7 5 6 4 (
0 . 0 1 7 4 )
15)
1 6 1 3 9 2 . 9 0 5 9 (
0 . 0 3 3 9 )
4 6 . 1 0 2
4 0 . 7 1 3
14)
1 6 7 3 6 0 . 8 4 3 4 (
0 . 0 0 4 3 )
49.120
4 3. 5 37
4)
154136 . 0941
( 1. 0)
154195.1535
(1.0)
1 5 4 2 6 1 . 4 6 33
(1. 0 )
154334.6527
( 1 . 0)
)
1 5 4 4 1 4 . 70 77
(0 . 0 )
353)
0 . 0 0 7 7
0 . 0 1 7 8
0 . 0 4 1 9
•0.0270
•0 . 0 4 8 7
2 2 6 . 5 7 7
2 2 1 . 4 3 3
2 2 6 . 5 7 7
2 2 1 .4 3 3
2 6 1 . 4 7 3
2 5 6 . 3 2 7
261
2 5 6 . 3 2 7
.473
2 9 9 . 2 7 3
2 9 4 . 1 2 5
2 9 9 . 2 7 3
294.
3 3 9 . 9 4 4
334.794
3 3 9 . 9 4 4
334.794
125
16 (
1
16)
-
15 (
1
15)
1 5 9 2 8 7 . 2 6 6 7 (
0 . 0 3 3 8 )
4 6 . 7 9 4
4 1 . 4 8 1
16 (
2
14)
-
15 (
2
13)
1 6 6 2 4 1 . 9 0 4 3 (
0 . 0 3 4 0 )
5 3 . 0 5 2
4 7 . 5 0 6
16
2
15)
-
15
2
14)
1 6 3 5 9 0 . 8 0 9 1 (
0 . 0 3 3 3 )
5 2 . 6 3 5
47.
16 (
3
13)
-
15 (
3
12)
1 6 4 5 5 6 . 5 6 4 0 (
0 . 0 0 3 5 )
60
5 5 . 0 1 2
(
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179
16 (
3
14)
-
15 (
3
13)
1 6 4 3 6 6 . 5 5 3 1 (
0 . 0 3 3 6 )
6 0 . 4 8 1
5 4 . 9 9 3
16
4
12)
-
15 (
4
11)
1 6 4 3 1 1 . 4 0 5 6 (
0 . 0 3 3 4 )
7 1 . 2 7 4
6 5 . 7 9 3
16 (
4
13)
-
15 (
4
12)
164306. 5023 <
0 . 0 0 3 4 )
7 1 . 2 7 4
6 5 . 7 9 3
16 (
5
11)
-
15 (
5
1 6 4 2 6 3 . 6 5 4 6 (
0 . 0 0 3 6 )
8 5 . 1 4 4
7 9 . 6 6 5
16 (
5
12)
-
15
(
10)
5
11)
1 6 4 2 6 3 . 5 9 0 3 (
0 . 0 0 3 6 )
8 5 . 1 4 4
1 6 (
6
10)
-
15 (
6
9)
1 6 4 2 6 0 . 0 3 6 0 (
0 . 0 3 4 1 )
1 0 2 . 0 7 9
96.
16 (
6
11)
-
15 (
6
10)
1 6 4 2 6 0 . 0 3 5 5 (
0 . 0 0 4 1 )
102
16 (
7
9)
-
15 (
7
8)
1 6 4 2 7 8 . 7 1 0 3 (
0 . 0 0 4 8 )
16 (
7
10)
-
15 (
7
9)
1 6 4 2 7 8 . 7 1 0 3 (
0 . 0 0 4 8 )
122.062
122.062
9 6 . 6 0 0
16 (
8
8)
-
15 (
8
7)
1 6 4 3 1 2 . P 3 9'3 (
0 . 0 0 5 4 )
1 4 5 . 0 7 3
1 3 9 . 5 9 2
16 (
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9)
-
15 (
8
8)
1 6 4 3 1 2 . 0 3 9 3 (
0 . 0 3 5 4 )
1 4 5 . 0 7 3
1 3 9 . 5 9 2
16
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7)
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15
(
9
6)
1 6 4 3 5 6 . 5 3 9 8 (
0 . 0 3 5 8 )
171.C92
165.610
16 (
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8)
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7)
1 6 4 3 5 6 . 5 3 9 3 (
0 . 0 0 5 8 )
1 7 1 . 0 9 2
165.610
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4)
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2 3 2 . 0 6 3
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600
1 1 6 . 5 8 2
1 1 6 . 5 8 2
194.
613
226.
577
1 6 ( 1 1
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5)
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2 3 2 . 0 6 3
2 2 6 . 5 7 7
16(12
4)
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3)
1 6 4 5 4 2 . 9 4 7 5 (
0 . 0 3 7 6 )
2 5 6 . 9 6 1
2 6 1 . 4 7 3
16(12
5)
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4)
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2 6 1 . 4 7 3
16
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2)
1 6 4 6 2 0 . 6 7 6 7 (
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3 0 4 . 7 6 4
2 9 9 . 2 7 3
(13
REMARKS
314
1 5 5 6 5 7 . 2 4 2 3 (
1 5 3 4 2 5 . 7 9 3 9 ( 1 . 0)
14 (
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n
TABLE I.
OBSERVED AND CALCULATED F R E Q U E N C I E S OF VINYL ISOCYANIDE
OBSERVED
CALCULATED
UPPER
LOWER
FREQUENCY
(STANDARD
STATE
STATE
(WEIGHT)
TRANSITION
FREQUENCY
DBS. -CALC«
DEVIATION)
IN MHz
ENERGY
(CONT INUE 0)
LEVELS
IN
CM-1
UPPER
LOWER
STATE
STATE
16(13,
4)
-
15
3)
164620.6767(
0 .0116)
16(14,
2)
15(14,
1)
164705.7527(
0 .0181)
304 .764
345 .438
299. 273
339. 944
15(14,
2)
164705.7527(
0 .0181)
345 .438
339. 944
15(15,
15(15,
0)
164798.0671(
1)
164798.0671(
0 .0275)
0 .0275)
388 . 9 5 1
338 . 9 5 1
383. 454
383. 454
171186.3290(
0 .0344)
0 .0049)
0 .0043)
51 . 8 1 2
55 . 0 4 6
52 . 4 3 7
46. 102
177685.0023<
58 . 9 5 1
16(14,
3)
-
16(15,
1)
-
16(15,
2)
-
(13,
17 (
0,17)
-
16 (
17 C
1,16)
-
16 (
17 (
1,17)
-
16 (
17(
2,15)
-
17 (
17(
2,16)
3,14)
-
17(
3,15)
17 C
17(
4,13)
4,14)
17(
a, 16)
l . 15)
l , 16)
171186 .3604(1 .0)
1 7 7 6 8 4 . 9 7 1 6 ( 1 . 0)
169163 .8916(1 .0)
16 (
16 (
2, 14)
1 7 6 8 4 6 . 3929 (1. 0 )
2, 15)
-
16 (
3, 13)
173743 .8150
174914 .8160
-
16 (
16 (
3, 14)
4, 12)
1 7 4 6 5 8 . 3 5 0 3 ( 1 . 0)
1 7 4 6 0 3 . 5 2 2 2 (1 . 0)
174658.3589(
174603.5246(
-
16 (
4, 13)
174596 .0032(1 .0)
174595.9990(
5,12)
-
16 (
174541 .3877
17 (
5,13)
-
174541.4455(
174541.3331(
17(
6,11)
-
16 (
16
5, 11)
5, 12)
17(
6,12)
-
16 (
17(
1 7 (
7,10)
7,11)
-
9)
8,10)
17 C 8 ,
17 (
(1. 0 )
173743.-8203 (
(1 . 0 )
174914.8164(
(0 . 0)
1 7 4 5 4 1 . 3 8 7 7 (0 . 0)
102. 079
122. 062
-
16 (
7, 10) /
174548.9850
(1 . 0 )
174548.9695(
0 . 0 0 6 0)
0 .0155
127 . 8 8 4
16 (
8,
8)
174582.3580(
122. 062
1 4 5 . C 73
-
16
9) f
7) t
174582.3478(1 .3)
174582 .3580 (
174628.2505(
0 .0369)
0.0069)
174628.2505(
c.0076)
174634.5148(
0 .0081)
174684.5143(
174749.9813(
0 .0081)
0. 0 0 8 7 )
(
(10,
174684.5393(1 .0)
-
6) I
7) f
5)
7)
-
16
6) f
174749.9975
5)
-
16(12,
17(12,
6)
-
16(12,
17(13,
4)
-
16(13,
17(13,
5)
-
17(14,
17(14,
3)
4)
-
16(13,
16(14,
-
16
17(15,
2)
-
16(15,
1)
(11,
(14,
\
(1. 0 )
3) i
4) /
\
\
(
2)
3) /
174749.9810(
0. 0 0 8 7 )
0 .0104)
(1. 0 )
174823.9747 (
174823.9747(
266. 961
310 . 5 9 8
304. 764
310 . 5 9 8
351 .276
304. 764
0 .0430)
0 .0002)
0 .0005)
Q
BRANCH
. 0066
. 0285
- 0 . 2028
-0
.3518
266. 961
345. 433
351 .276
345. 438
394 . 7 9 1
388. 951
394 .791
388. 951
441 .110
435. 266
441 .110
435. 266
1 .897
1. 379
2 .598
3 .650
2. 546
3. 547
5 .053
6 .806
4. 880
6. 5 4 7
* *
1 (
2(
1 ,
1,
0)
1)
-
1(
1,
1)
517.5954(
-
2 (
1,
2)
1 5 5 2 . 7 5 9 7 {
3 (
1,
2)
-
3 (
1,
3)
3105.4177(
4 (
5 (
1,
1,
4)
5175.3996(
0 .0310)
0 .0317)
5)
7762. 3735 (
0 .0324)
-
6 (
7 (
1,
1,
6)
7)
-
8 (
9 (
-
10 (
-
11 (
8)
1,
9)
1,
1, 10)
1, 11)
1,
8)
1,
9)
1,10)
272 .793
-0
175199.3069(
1 7 5 1 9 8 . 9 5 5 1 ( 0 . 0)
8 (
232. 063
0 .0430)
1) {
-
237 .892
2 72 . 7 9 3
175199.3069(
. 0)
16
5)
6)
7)
0. 0 1 6 5
0 .0302)
0 .0302)
-
1,
1,
1,
200. 097
232. 063
175093.8671(
175Ö93.8671(
2)
6 (
20 0. 0 9 7
205 .924
237 .892
-0 .1240
17(16,
-
205 .924
174995 .9320(0 .0)
175093.6643(0
171. 092
0 . 0245
0 .0206)
0.0206)
2) j
0)
-
171. 092
174996.1060(
174996.1360(
16(16,
4)
176 .917
.0111
-0
16(15,
3)
-0
0 .0141)
-
1,
1 4 5 . 0 73
174906. 0959 (
-
1,
150 . 8 9 6
176 . 9 1 7
174906.0674(1 .0)
3)
4(
-0 .0102
174906.0959(
1)
5 (
150 . 8 9 6
0.0104)
0 .0141)
174823. 9 6 8 1
17(15,
(16,
0 .0076)
(1. 0 )
)
4)
5) f
17(16,
9(
10(
11(
85. 144
85. 144
16 (
16 ( 1 0 ,
16(11,
TYPE
71. 274
90 . 9 6 6
90 . 9 6 6
1G 2 . 0 7 9
16
A
77 . 0 9 8
107 . 9 0 1
127 .884
-
**
0 . 0042
-0 . 0578
0 .0546
60. 501
107 .901
-
17(12,
60. 481
71. 274
-0 . 0098
174628 .2394
17(11,
66 . 3 3 6
66 . 3 0 7
77 . 0 9 8
0 .0051)
0 .0060)
8) j
6)
-0 . 0004
-0 .0186
-0 . 0024
174532.2684(
174548.9696 (
9,
17(11,
0 .0044)
5 3. 052
52. 635
174532.2694(
16 (
7)
8)
0 .0041)
0 .0341)
58 . 4 3 1
(1 . 0 )
16 (
17(10,
17(10,
0.0342)
-0 . 0058
174532.2586
-
8)
9)
0047)
49. 120
46. 794
6, 10) I
6, 11) f
7,
9) 1
-
9,
9,
0 .
0 .0044)
0 .0042)
-G . 0 0 1 7
0 . 0065
0 .0044)
0 .0351)
8,
9,
17 (
17 (
169163.8933(
176846.3864(
0 . 0314
-0 .0307
REMARKS
1C865 .7605
14484 .5980
(1 . 0)
10865.7548(
(1
14434.5939 (
. 0)
1 8 6 1 7 . 7 3 0 0 (0 . 0 )
18617.4419 (
23262.1958(
28415.9235 (
34074.6710 (
0 .0032)
0 .0041)
0.
0 .0049)
0 .0058)
0 .2881
0 .0 066)
0 .0074)
0057
0 .0041
8 .909
8. 546
11 . 3 6 2
14 . 1 6 5
10. 879
13. 544
16. 541
17 . 3 1 7
20 . 8 1 7
24 . 6 6 7
1 9 . 8 6 9 Unauthenticated
23. 530
Download Date | 10/2/16 10:01 AM
O
T A B L E I.
OBSERVED AND C A L C U L A T E D F R E Q U E N C I E S OF VINYL ISOCYANIDE
OBSERVEO
CALCULATED
UPPFR
LOWER
FREQUENCY
(STANDARD
STATE
STATE
(WEIGHT)
TRANSITION
FREQUENCY
OBS . - C A L C .
DEVIATION)
IN MHz
ENERGY
(CONT INUE 0)
LEVELS
IN
CM-:
UPPER
LOWER
STATE
STATE
8 (
2,
6»
_
8 (
2,
7)
90 5 . 4 9 6 3 (
0.0011)
18
9 (
2.
7)
-
9 (
2,
8)
1419. 1283 (
0.0015)
21.618
9)
.525
18. 494
21. 571
10 (
2.
8)
-
10 (
2,
2121. 0821 (
0.0021)
2 5 . 0 5 9
24. 988
11(
2,
9)
-
11 (
2 , 1 0 )
3 0 4 9 . 5 3 1 9 (
0.0028)
28.848
28. 746
32. 844
12(
2,10)
-
12 (
2 , 1 1 )
4 2 4 4 . 1 6 4 1 (
0.0336)
3 2 . 9 8 6
13(
2,11)
-
13 (
2,12)
5 7 4 5 . 2 1 4 8 (
0.0344)
3 7 . 4 7 4
37. 283
14(
2,12)
-
14 <
2,13)
7592.4046 (
0.0052)
4 2 . 3 1 4
42. 061
15 (
2,13)
-
15 (
2 , 1 4 )
9 8 2 3 , 8 4 1 5 ( 1 . 0 )
9823.8361 (
0.0059)
0 .
16(
2,14)
-
16 (
2,15)
1 2 4 7 4 . 9 3 5 5 ( 1 . 0 )
1 2 4 7 4 . 9 3 1 8 (
0.0365)
0 .00
1 5 5 7 7 . 4 9 8 5 ( 1 . 0 )
1 5 5 7 7 . 4 9 7 4 (
1 9 1 5 8 . 9 8 1 7 (
0.0069)
0 .0011
17(
2,15)
-
17 (
2,16)
1 8 (
19 (
2,16)
2,17)
-
2,
-
18 (
19 (
2 , 1 8 )
17)
2 3 2 4 1 . 9 8 2 0 (
0054
37
4 7 . 5 0 6
47. 179
5 3 . 0 5 2
52. 635
58.951
58. 431
0.0072)
0.0075)
6 5 . 2 0 4
64. 565
7 1 . 8 1 1
71. 036
17 (
3,14)
_
17 (
3 , 1 5 )
8 6 2 . 2 2 5 9 (
0.0327)
6 6 . 3 3 6
66. 307
18 (
3,15)
-
18 (
3 , 1 6 )
1201.9480 (
0.0034)
72.516
72. 476
19 (
3,16)
-
19 (
3,17)
1 6 4 4 . 4 2 4 3 (
0.0041)
79.044
78. 989
20 (
3 , 1 8 )
2211.9187(
0.0349)
85.918
85. 84^
21 (
3 , 1 9 )
2929. 5024 (
0 . 0 0 5 7 )
9 3 . 1 4 1
93. 044
100. 586
20 C
3,17)
21 (
3,18)
-
22 (
3,19)
-
22 (
3,20)
3 8 2 5 . 0 0 1 2 (
0.0364)
1 0 0 . 7 1 3
23 (
3,20)
-
23 (
3 , 2 1 )
4 9 2 8 . 8 3 9 0 (
0.0370)
1 0 8 . 6 3 5
108. 471
24(
3,21)
-
24 (
3,22)
6 2 7 3 . 7 6 0 3 (
0 . 0 0 7 4 )
1 1 6 . 9 0 8
116. 698
7894.4224 (
0.0075)
1 2 5 . 5 3 2
125. 268
9826.8517 (
0.0374)
-0 . 0027
1 3 4 . 5 0 9
134. 181
143
1 5 3 . 5 2 4
1 5 3 . 0 31
1 6 3 . 5 6 5
162. 969
25 (
3,22)
-
25 (
26 (
3,23)
-
26 1
3,23)
3,24)
27 (
3,24)
-
27(
28 (
3,25)
-
29 (
3,26)
-
3,25)
9 8 2 6 . 8 4 9 0 ( 1 . 0 )
1 2 1 0 7 . 7 6 8 5 ( 1 . 0 )
1 2 1 0 7 . 7 7 0 5 (
0.0371)
28 (
3,26)
1 4 7 7 3 . 7 7 7 0 ( 1 . 0 )
1 4 7 7 3 . 8 1 4 3 (
0.0070)
-0 .0020
-0 .0373
29 (
3,27)
1 7 8 6 0 . 6 6 2 5 ( 1 . 0 )
1 7 8 6 0 . 6 7 0 7 (
0 . 0 0 7 6 )
-0 .0082
37 (
4,33)
_
37 <
4 , 3 4 )
8 1 6 6 . 5 6 0 0 ( 1 . 0 )
8166.5540(
38 (
4,34)
-
38 (
4 , 3 5 )
9 9 3 8 . 6 3 6 0 ( 1 . 0 )
9938.6343
39 (
4,35)
-
39 (
1 2 0 1 3 . 4 9 8 3 (
4,36)
-
40 (
4 , 3 6 )
4 , 3 7 )
1 2 0 1 3 . 5 0 1 0 ( 1 . 0 )
40 (
1 4 4 2 6 . 0 0 0 5 ( 1 . 0 )
14425.9893(
41 (
4,37)
-
41 (
4 , 3 8 )
1 7 2 1 1 . 7 2 3 5 ( 1 . 0 )
17211.7178 (
2 6 6 . 0 7 1
265. 799
2 7 9 . 1 7 9
278. 848
0.0079)
0 .0027
2 9 2 . 6 4 0
292. 239
0.0097)
0 .0112
3 0 6 . 4 5 6
305. 975
0.0128)
0 .
3 2 0 . 6 2 7
320. 053
4 7 6 . 2 5 8
475. 960
50 (
5,45)
50 (
5 , 4 6 )
8 9 2 3 . 0 1 7 5 ( 1 . 0 )
8923•0164(
5,
46)
-
51 (
5,47)
1 0 6 7 4 . 1 0 6 0 ( 1 . 0 )
1 0 6 7 4 . 1 2 6 7 (
0 .0120 )
5 2 (
5,47)
-
52 (
5 , 4 8 )
12705.6035 (1.
1 2 7 0 5 . 6 0 2 5 (
0.0109)
53 (
5,48)
-
53 (
5,49)
1 5 0 4 9 . 7 8 0 5 ( 1 . 0 )
15049.7884
54 (
5,49)
-
54 (
5 , 5 0 )
1 7 7 4 0 . 3 8 4 0 ( 1 . 0 )
1 7 7 4 0 . 3 7 9 6 (
0.0198)
P
BRANCH
**
B
TYPE
0.0130)
(
143. 435
0 . 0060
0 .0017
0.0079)
( ,0.0075)
51 (
0)
.839
0.0123)
0057
0 .0011
- 0 .
0207
0 .0010
-0 .
0079
0 .0044
4 9 3 . 8 3 9
493. 483
5 1 1 . 7 7 2
511. 349
530.060
529. 558
5 4 8 . 7 0 3
548. 112
1,
1)
-
2 (
0 ,
2)
2 5 5 8 2 . 8 3 0 0 ( 1 . 0)
2 5 5 8 2 . 8 8 0 8 (
0.0330)
- 0 . 05 0 8
1 . 8 7 9
1. 0 26
2 (
1,
2)
-
3 (
0,
3)
1 4 8 2 7 . 6 ; 0 0 ( 1 . 0)
1 4 8 2 7 . 6 3 0 8 (
0.0329)
- 0 . 0008
2 . 5 4 6
2. 052
3. 419
3 (
1,
3)
-
4 (
0,
4)
3837.2868(
0.0030)
3 . 5 4 7
5 (
0,
5)
-
4 (
1,
4)
7373»
0.0032)
5 . 1 2 6
6 (
6)
-
5 (
1,
5)
1 8 7 8 8 . 9 2 0 0 ( 0 . 0)
1 8 7 8 8 . 8 2 6 5 (
0.0035)
7 (
o,
0,
7)
-
6 (
1,
6)
• 3 0 3 8 6 . 7 5 0 0 ( 1 . 0)
3 0 3 8 6 . 7 4 0 4 (
0.0337)
8 (
0,
8)
-
7 (
1,
7)
4 2 1 4 4 . 3 0 1 6 (
9 (
9)
0,
0 , 10)
-
8 (
1,
8)
5 4 0 3 5 . 4 1 6 5 (
0.0040)
0.0043)
-
9 (
1,
9)
66031.7383(
0.0045)
0 , 11)
0, 12)
-
10 (
0.0047)
2 2 . 4 7 5
19. 369
-
11(
1, 10)
1. 11)
7 8 1 0 3 . 2 2 7 5 (
9 0 2 1 8 . 8 6 3 4 (
0.0348)
2 6 . 5 3 9
2 3. 530
_
10 (
1,
2 2 5 3 4 . 5 4 4 7 (
0.0378)
11(
12 (
9 (
2,
8)
O
**
1(
10 (
REMARKS
9)
9 0 2 1 8 . 8987
(1. 0)
9889(
0. 0935
0. 0 0 9 6
0. 0353
a
4. 880
7 . 1 7 4
6. 5 4 7
a
9 . 5 6 0
8. 546
a
1 2 . 2 8 5
10. 879
1 5 . 3 4 6
13. 544
1 8 . 7 4 3
16. 541
21.571
Unauthenticated
20. 817
Download Date | 10/2/16 10:01 AM
TABLE I.
OBSERVED
AND C A L C U L A T E D F R E Q U E N C I E S OF VINYL I S O C Y A N I D E
OBSERVED
CALCULATED
UPPER
LOWER
FREQUENCY
(STANDARD
STATE
STATE
(WEIGHT)
TRANSITION
10(
2,
-
11(
1
10)
12(
1,11)
-
11 (
2
10)
13 (
1,12)
-
12 (
2
11)
14(
1,13)
-
13 (
2
15 (
1,14)
-
14 (
20 (
1,19)
-
19 (
9)
FREQUENCY
IN
CM-1
LOWER
STATE
STATE
24. 667
28. 746
33 . 4 0 8
32. 844
0 . 0 0 3 3 )
38 . 3 0 0
37. 283
0 . 0 0 8 5 )
43 . 5 3 7
42. 061
74 . 8 8 4
71. 036
0 . 0 0 8 0 )
1 6 9 1 4 . 5 0 5 6 (
0 . 0 3 8 1 )
12)
3 0 4 3 9 . 2 6 5 2 (
2
13)
4 4 2 5 0 . 5 8 5 3 (
2
18)
5 5 ( 1 . 0 )
LEVELS
UPPER
28 . 8 6 4
0 . 0 3 7 9 )
3 5 3 7 . 5 9 0 3 (
16914 .50
ENERGY
(CONT INUE 0)
24 . 9 8 8
9 6 3 1 . 6 1 9 9 (
9631 . 6 1 5 0 ( 1 . 0 )
OBS.-CALC.
DFVIATION)
IN M H z
115343 .9007
( 1 . 0 )
1 1 5 3 4 3 . 9 2 3 7 (
0 .
0123)
(1.0)
0096)
-0 . 0 0 4 9
-0 .
- 0 .
0001
0230
17 (
2,15)
_
18 (
1
18)
16239 .7515
1 6 2 3 9 . 7 4 5 3 (
0 .
0 .0062
58 . 9 5 1
58. 409
18 (
2,16)
-
19 (
1
19)
14821 . 3 6 6 0 ( 1 . 0 )
1 4 3 2 1 . 3 5 2 2 (
0 . 0 3 9 6 )
0 . 0 1 3 8
65 . 2 0 4
64. 709
19 (
2,17)
-
20 (
1
20)
14187 . 6 7 4 5 ( 1 . 0 )
1 4 1 8 7 . 6 8 6 1 (
0 . 0 3 9 6 )
- 0 . 0 1 1 6
71 . 8 1 1
71. 338
20 (
2,18)
-
21 (
1
21)
14352 . 8 5 1 0 ( 1 . 0 )
1 4 3 5 2 . 8 5 1 5 (
0 . 0 0 9 8 )
- 0 . 00 05
78 . 7 7 4
78. 295
21 (
2,19)
-
22 (
1
22)
1 5 3 2 4 . 9 9 4 1 (
0 . 0 1 1 2 )
86 . 0 9 1
85. 580
22 (
2,20)
-
23 (
1
23)
1 7 1 0 6 . 5 1 1 6 (
0 . 0 1 4 8 )
23 (
2,21)
-
24 (
1
24)
1 9 6 9 4 . 4 1 9 0 (
0 . 0 2 1 8 )
13 (
3,10)
-
14 (
2
13)
90173 . 3409 (1.
90173. 8124 (
0 . 0 1 4 2 )
22 (
3,19)
_
23 (
2
22)
12663 . 3 1 4 ^ ( 1 . 0 )
23 (
3,20)
-
24 (
2
23)
5 72 0 • 4 7 4 6 (
0 . 0 0 7 0 )
108 . 6 3 5
103. 444
25 (
2 , 2 4 )
-
24 (
3
21)
7 4 4 . 2 9 8 7 (
0 . 0 3 7 5 )
116 . 9 3 2
116. 908
6 6 8 6 . 7 1 7 9 (
0 . 0 3 8 6 )
125 . 7 5 5
125. 532
1 7 1 0 6 . 50 6 0 ( 1 . 0 )
0)
26 (
2,25)
-
25 (
3
22)
27 (
2,27)
-
26 (
3
23)
12062 . 0 5 2 5 ( 1 . 0 )
1 2 0 6 2 . 0 4 4 6 (
2 8 (
2,27)
-
27 (
3
24)
1 6 8 2 5 . 8260 (1.
1 6 3 2 5 . 8 2 5 6
28 (
4,25)
-
29 (
3
26)
0)
8410 . 3 9 5 0 ( 1 . 0 )
0 .
1 2 6 6 3 . 3 1 8 3 (
(
0371)
- 0 .
0056
93 . 7 6 2
101 .787
0 .
0285
- 0 .
0038
93. 192
101.
130
45 . 0 6 9
42. 061
1G 0 . 7 1 3
1C0. 291
0 . 0 1 0 6 )
0 . 0 0 7 9
134 .911
134. 509
0 . 0 1 3 5 )
0 .
0004
144 . 4 0 1
143.
- 0 . 00 38
163 . 8 4 5
163. 565
183. 866
8 4 1 0 . 3 9 8 8 (
0 . 0 1 4 4 )
839
30 (
4,26)
_
31 (
3
29)
8427 . 5350 (1.
0)
8 4 2 7 . 5 4 5 6 (
0 . 0 1 1 3 )
- 0 . 0 1 0 6
134 . 1 4 7
29 (
4,25)
-
30 (
3
28)
17742 . 8355 (1.
0)
1 7 7 4 2 . 8 4 3 9 (
0 . 0 1 1 9 )
- 0 .
173 .839
17 3 . 2 4 7
33 (
3,31)
-
32 (
4
28)
9 4 9 7 . 7 7 2 4 (
0 . 0 1 2 7 )
- 0 . 0 1 1 9
236 . 1 2 3
2 C 5. 307
- 0 . 00 3 6
9497 . 7 6 0 5 ( 1 . 0 )
0084
37 (
5,33)
_
38 (
4
34)
10488 . 2 4 4 5 ( 1 . 0 )
1 0 4 8 8 . 2 4 8 1 (
0 . 0 1 3 8 )
40 (
4,
-
39 (
5
35)
14971 . 3055 (1.
1 4 9 7 1 . 7 9 9 0
(
0 . 0 1 4 4 )
38 (
5,33)
_
39 (
4
36)
0 . 0 1 4 8 )
4,38)
-
40 (
5
35)
1 0 5 9 1 . 0740 ( 1 . 0 )
9847 . 5 9 6 5 ( 1 . 0 )
1 0 5 9 1 . 0 6 2 4 (
41 (
9 8 4 7 . 5 9 7 4 (
0 . 0 1 9 4 )
46 (
6,41)
_
47 (
5
42)
11340 . 4 1 2 0 ( 0 . 0 )
11340 .4586 (
0 . 0 9 3 4 )
- 0 . 0 4 6 6
49 (
5,44)
-
48 (
6
43)
12783 . 3075 (0.
1 2 7 8 3 . 7 2 2 5 (
0 . 0 9 2 2 )
0 .
0850
46 (
6,40)
_
47 (
5
43)
16652 .6210
(0.0)
1 6 6 5 2 . 6 5 8 0 (
0 . 0 9 1 2 )
- 0 .
0370
426 . 0 1 5
425. 459
50 (
5,46)
-
49 {
6
43)
15707 . 7480 (0. 0 )
1 5 7 0 7 . 6 4 3 7 (
0 . 1 0 0 3 )
475 .960
475. 436
Q
BRANCH
**
P
36)
TYPE
0)
0)
279 . 5 2 9
279. 179
0065
306 . 4 5 6
305. 956
0 .
0116
292 . 5 9 3
292.
- 0 .
0009
320 . 0 5 3
319. 724
426 .006
425. 623
459 .030
458. 603
0 .
0 . 1 0 4 3
REMARK»
239
* *
1(
1,
0)
_
1 (
0,
1)
4 6 6 0 7 . 2 4 0 4 (
c
. 0 0 3 4 )
1 .897
0. 342
2 (
1)
-
2 (
0 . 0 0 3 4 )
2 .598
1,
2)
3(
2)
-
1,
47129. 5567 (
3(
1,
0,
3)
4 7 9 2 1 . 1 1 1 9 (
0 .
3 .650
1.
2.
4 (
1,
3)
-
4 (
0,
4)
48991. 5567 (
0 . 0 0 3 4 )
5 .053
5 (
<*)
-
5 (
0,
5)
5 0 3 5 3 . 6 6 1 3 (
0 . 0 0 3 5 )
6
.806
6 (
1,
1,
5)
-
6 (
0,
6)
5 2 0 2 3 . 1 9 9 2 (
0 . 0 0 3 7 )
8 . 9 0 9
7 (
1,
6)
-
7 (
0,
7)
54018. 7477 (
0 . 0 0 3 9 )
11 . 3 6 2
9. 560
8 (
1,
7)
-
8 (
0,
8)
5 6 3 6 1 . 3 9 7 1 (
0 . 0 0 4 2 )
14 . 1 6 5
12. 235
9 (
1,
8)
-
9 (
0»
9)
5 9 0 7 4 . 3 2 3 4 (
0 . 0 3 4 5 )
17 . 3 1 7
0334)
026
052
3. 4 1 9
5.
126
7. 174
Unauthenticated
15. 346
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T A B L E I.
OBSERVED
TRANSITION
AND CALCULATED FREQUENCIES OF VINYL ISOCYANIDE
OBSERVED
CALCULATED
(STANOARO
UPPER
LOWER
FREQUENCY
STATE
STATE
(WEIGHT)
10 (
-
10 F
0 , 1 0 )
FREQUENCY
OBS.-CALC.
DEVIATION)
IN MHz
(CONT INUE 0)
ENERGY
UPPER
STATE
6 2 1 8 2 . 2 1 1 4 (
0 . 0 0 4 9 )
LEVELS
IN
CM-:
ST A T E
2 0 . 8 1 7
18. 743
11<
1»
9)
1,10»
-
I K
0 , 1 1 )
6 5 7 1 0 . 5079 (
0.
2 4 . 6 6 7
22. 475
12 (
1.11)
-
12 {
0 , 1 2 )
6 9 6 8 4 . 5 2 7 2 ( 1 . 0 )
6 9 6 8 4 . 5 0 7 9 (
0 . 0 0 5 8 )
0 . 0 1 9 3
2 8 . 8 6 4
26. 539
16 (
1 , 1 5 )
-
16 (
0 , 1 6 )
9 0 4 7 6 . 4 0 6 4 ( 1 . 0 )
9 0 4 7 6 . 4 0 5 5 (
0 . 0 0 8 0 )
0 . 0 0 0 9
49
46.
23 (
1,22)
-
2 3 (
0 , 2 3 )
1 4 6 6 8 9 . 7 1 5 2 ( 1 . 0 )
1 4 6 6 8 9 . 7 0 8 3 (
0 . 0 1 6 8 )
0 .
9 7 . 7 8 1
92. 888
24. 667
0053)
0069
.120
102
11(
2,
-
11 (
1 , 1 0 )
1 2 5 3 4 0 . 6 2 2 7 ( 1 . 0 )
1 2 5 3 4 0 . 6 4 1 9 (
0 . 0 0 6 9 )
- 0 . 0 1 9 2
2 8 . 8 4 8
12 (
2,10)
-
12 (
1 , 1 1 )
1 2 3 5 7 2 . 1 7 7 2 ( 1 . 0 )
1 2 3 5 7 2 . 1 8 6 5 (
0 . 0 0 6 8 )
-0
3 2 . 9 8 6
28. 8 64
13 (
2,11)
-
13 (
1 2 1 8 9 3 . 2 6 0 5 ( 1 . 0 )
1 2 1 8 9 3 . 2 2 8 0 (
0.
33. 408
9)
0067)
. 0 0 9 3
14(
2,12)
-
14 (
1 , 1 2 )
1 , 1 3 )
1 2 0 3 5 2 . 6 3 3 8 ( 1 . 0 )
1 2 0 3 5 2 . 6 2 6 1 (
0 . 0 3 6 6 )
0 . 0 0 7 7
3 7 . 4 7 4
4 2 . 3 1 4
1 5 (
2 , 1 3 )
15 (
1 , 1 4 )
1 1 8 9 9 9 . 0 6 4 5 ( 1 . 0 )
1 1 8 9 9 9 . 0 6 2 1 (
0 . 0 0 6 6 )
0 .
4 7 . 5 0 6
43. 537
16 C
2,14)
-
16 (
1 , 1 5 »
1 1 7 8 8 0 . 1 2 0 4 ( 1 . 0 )
117*8 0 . 1 2 3 4 (
0 . 0 0 6 6 )
- 0 . 0 0 3 0
5 3 . 0 5 2
49. 120
17 (
2,15)
1 , 1 6 )
1 1 7 0 4 1 . 0 5 8 9 ( 0 . 0 )
1 1 7 0 4 1 . 5 0 7 4 (
0 . 0 0 6 6 )
- 0 . 4 4 8 5
5 8 . 9 5 1
55. 046
2,16)
-
17 (
18 (
18 C
1 , 1 7 )
1 1 6 5 2 6 . 3 4 0 0 ( 1 . 0 )
1 1 6 5 2 6 . 4 0 8 6 (
0 . 0 0 6 5 )
- 0 . 0 6 8 6
6 5 . 2 0 4
61. 317
19 (
2,17)
-
19 (
1 , 1 8 )
1 1 6 3 7 5 . 1 7 3 0
1 1 6 3 7 5 . 1 2 6 4 (
0 . 0 3 6 4 )
0 . 0 4 6 6
7 1 . 8 1 1
67. 930
20 (
2,18)
-
20 (
1 , 1 9 )
1 1 6 6 2 4 . 9 2 5 7 ( 1 . 0 )
1 1 6 6 2 4 . 8 9 8 4 (
0 . 0 3 6 2 )
21 (
2 , 1 9 )
-
21 (
1 , 2 0 )
1 1 7 3 0 9 . 8 7 9 8 ( 1 . 0 )
1 1 7 3 0 9 . 9 2 4 5 (
0 . 0 J 6 0)
22 (
1 , 2 1 )
1 1 8 4 6 1 . 5 3 3 6 ( 1 . 0 )
1 1 8 4 6 1 . 5 2 3 5 (
0 . 0 3 6 3 )
0 . 0 1 0 1
9 3 . 7 6 2
89. 811
23 (
1 , 2 2 )
1 2 0 1 0 8 . 3 3 9 7
1 2 0 1 0 8 . 3 4 2 0 (
0 . 0 0 7 3 )
- 0 . 0 0 2 3
1 0 1 . 7 8 7
97. 781
(1.
0)
0 . 0 3 2 5
0024
38. 300
0 . 0 2 7 3
7 8 . 7 7 4
74. 884
- 0 . 0 4 4 7
8 6 . 0 9 1
82. 178
22 (
2 , 2 0 )
23 (
2,21)
24(
2 , 2 2 )
-
24 (
1 , 2 3 )
1 2 2 2 7 6 . 5 5 3 7 ( 1 . 0 )
1 2 2 2 7 6 . 5 3 7 9 (
0 . 0 3 9 1 )
0 . 0 1 5 8
25 (
2 , 2 3 )
-
25 (
1 , 2 4 )
1 2 4 9 8 9 . 8 6 0 9 ( 1 . 0 )
1 2 4 9 8 9 . 8 6 5 7 C
0 . 0 1 1 6 )
- 0 . 0 0 4 8
1 1 8 . 8 9 8
114. 728
R
BRANCH
1 1 9 4 2 2 . 4 1 7 9 ( 1 . 0 )
1 1 9 4 2 2 . 4 1 0 7 (
0 . 0 3 5 9 )
0 . 0 0 7 2
1 3 . 5 4 4
9. 560
* *
8 (
B
TYPE
1,
8)
-
7 (
0,
(1.
0)
110
. 1 6 6
REM AR KS
LOWER
106.
087
**
7)
a) Reported in Ref.(5).
b) Unresolved K-doublet.
c) Several lines are overlapping.
d) Partially resolved K-doublet.
e) Not used in the fit: poor measurement.
f) Not used in the fit: Higher order centrifugal distortion correction
might be necessary.
g) Not used in the fit.
Unauthenticated
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K. Yamada and M. Winnewisser • Centrifugal Distortion Constants of Vinyl Isocyanide 686
686
Table II. Spectral parameters of vinyl isocyanide for
Watson's reduced Hamiltonian in V axis presentation.
51479.4578(30)
A
4868.94021 (25)
MHz
2.47615(63)
- 1 0 0 . 0 0 8 2 (69)
3421.08(40)
0.549200(89)
27.203 (20)
kHz
kHz
kHz
kHz
kHz
0.00860(55)
- 0 . 4 4 4 (68)
4.08(22)
328.6(118)
0.00329 (23)
0.326(98)
50.6(75)
HJ
HJR
HKJ
HK
hj
HJK
HK
* =-0.977786
a
in the last column are obtained f r o m the observed xx
and r 2 , and the two linear combinations of the three
equations, ( 3 ) , ( 4 ) , and ( 5 ) ,
(C2/A2)
rbbcc
(6)
raabb + (C2/B2) xbbbh,
(7)
Ar'cccc = 0
(8)
r 2 , and x'cccc.
The ob-
tained variations of the constants are not large f o r
the V —NC molecule, but considerably larger than
the estimated errors originating f r o m the standard
errors of the spectroscopic constants listed in Table
IO"3
Table III. Watson's determinable rotational constants and
quartic centrifugal distortion constants a for vinyl isocyanide.
51479.4628(30)
5386.49800(25)
4868.90066(25)
-13.2942(16)
- 1 4 . 2 9 8 2 (26) x 10~ 3
— 5.5110(26)x I O " 3
0.370319(29)
24.2529 (35) x I O " 3
-0.1334(ll)x IO-3
T2/(2I+23+£)
A x'cccc b
+ {C2/B2)xaabb,
relating the observed xx,
The standard deviation of the fit is 19.5 kHz for 173
equally weighted lines. Numbers in parentheses are
standard errors.
21
23
e
t'aaaa — ^ Xaaaa
r'bbbb^W
rbbbb
x'cccc = fr4 Xcccc
= (C2/A2)
laaaa
which are linearly independent with
Hz
Hz
Hz
Hz
Hz
Hz
Hz
6P=-5.58457 x
in the fourth column are obtained by the use of
Eqs. ( 3 ) and ( 5 ) , and the observed x x and r 2 . Those
MHz
MHz
C
Aj
AJK
AK
<5/
(5K
a
5386.64856(25)
B
Eqs. ( 3 ) and ( 4 ) , and the observed xx and r 2 . Those
MHz
MHz
MHz
MHz
MHz
MHz
MHz
MHz
MHz
II. Since we have no means to eliminate the vibrational effect f r o m these constants, the obtained constants f o r the various methods are listed parallel with
each other. The differences between the constants
obtained f r o m the different methods exemplify the
fact that such variations are proportional to r-defect
as discussed by the present authors
18.
It should be noted that we used the determinable
rotational constants, 91, S3, and (£, for the ground
vibrational state obtained in the present study in the
planarity conditions, Eqs. ( 3 ) — ( 7 ) , instead of the
equilibrium rotational constants.
Excluding all contributions of centrifugal distor-
Numbers in the parentheses are estimated errors on the
basis of the standard error of spectral constants in
Table II.
b r-defect: AT'CCCC=T'CCCC- (R2-& RJ/(2T + 23).
tion f r o m the determinable rotational constants, the
we can determine the four constants, raabb ,
effective moments of inertia and the inertia defect
a
rccaa,
and xabab,
tbbcc»
which do not vanish f o r a planar
molecule. Since the r-defect does not vanish in the
present case, different values are obtained f o r these
four constants depending on the way the planarity
conditions are used as pointed out b y Kirchhoff
15
and Cook et alias 1 6 ' 1 7 . However, the specific equations used have not been explicitly stated by these
authors. In order to show the differences among the
various methods clearly, the methods used in the
present analysis are compared here. The constants in
the first column of Table I V are obtained b y the
use of Eqs. ( 3 ) , ( 4 ) , and ( 5 ) , and the observed
xx.
Those in the second column are obtained b y the use
of Eqs. ( 3 ) ,
( 4 ) , and ( 5 ) , and the observed
r2.
Those in the third column are obtained by the use of
effective rotational constants in the ground state,
which are represented as a,
ß', and y of Kivelson
und Wilson 7 , are obtained as listed in Table IV. The
determined f r o m these constants are also listed in
Table I V .
b) Validity of the Reduced
and Choice of Axis
Hamiltonian
Representation
From the infinite number of unitary transformations which can be applied to the effective rotational
Hamiltonian we want to choose an appropriate one,
by which we mean one which reduces the number of
spectral constants to the number of determinable
parameters following Watson's discussion 6 . Next,
we have to check that the transformation does not
generate unignorable higher order terms with contributions above up to sextic terms, because we hope
to truncate the Hamiltonian as in Equation ( 1 ) . This
Unauthenticated
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687
K. Yamada and M. Winnewisser • Centrifugal Distortion Constants of Vinyl Isocyanide
tion, the order of magnitude of s m is 1 0 - 5 , which is
considerably larger than the upper limit of s n i for
convergence of the power series expansion of the
reduced Hamiltonian. Almost the same result is obtained in the II r axis representation.
check can be done by numerically evaluating s m ,
which is the coefficient of the unitary transformation,
as discussed by Watson 6 . Such a check was carried
out for various molecules by Carpenter 19 and Creswell and Mills 20 .
The unitary transformation used in the present
analysis is the one originally proposed by Watson 6
which reduces R 6 to zero and gives the Hamiltonian
shown in Equation ( 1 ) . The s l u for this transformation can be calculated on the basis of the r's by the
use of
sin = 4Rj(X-Y)
(9)
where
R6
= (T x x x x 4 - 1
yyyy
— 2 r xxyy) / 6 4 .
The reduction which makes R5 = 0 instead of
R 6 = 0 is one of the other possibilities of the reduction process 2 t ' 22 . For this reduction s m is expressed
as
R§
(10)
=
—
(T
Case 1 b
Case 2
ft4r aabb
h* tbbcc
h4T ccaa
abab
a'
ß'
/
la S
Ib S
Ic S
A
Re x 10 6
S m x 10®
0.34875(10)
-8.563(3)
0.16603(8)
-67.95(10)
51479.4585(30)
5386.58101(25)
4869.00709(25)
9.81704
93.8213
103.7945
0.156132(7)
-41.9
0.324
0.34875(10)
-8.563(3)
0.16603(8)
-67.19(10)
51479.4585(30)
5386.58101(25)
4869.00784(25)
9.81704
93.7213
103.7945
0.156116(7)
-41.9
0.324
c
Case 3
yyzz)
/32
10-7
and is calculated to be of the order
for the
present molecule in the I r axis representation. This
value is the same order of magnitude as that of the
unitary transformation used in the present analysis.
Since the reduction giving R6 = 0 is computationally
simpler, we conclude that the present choice of the
unitary transformation is the best among those
considered above.
c) Hyperfine
Structures
No nuclear quadrupole hyperfine structure could
be observed, although the lines are fairly broad at
low sample pressure. The full width at half maximum
of the line 1 0 1 ^ - O 0 0 is 0.35 MHz at a sample pressure of 2.5 x 1 0 _ 3 t o r r . Bolton et al. 5 also reported
that no hyperfine structure was observed. In general
the nuclear quadrupole hyperfine splitting caused by
Constants derived from planarity
Constant
— 2 T zzxx + 2 T
— X yyyy
x x x x
(12)
Rewriting Eqs. (9) and (10) in the I r axis representation, which has been used in the present analysis,
the s m coefficient was obtained for the unitary
transformation used in the present analysis for each
set of r's as listed in Table IV, and they are reasonably small indicating the validity of the reduction.
The I r axis representation is the best choice of axis
system for the present molecule, V — NC, a near
prolate top, if only the rigid rotor Hamiltonian is
considered. In the reduction of the effective rotational Hamiltonian, however, the I r representation
is not always the best choice of axis system 19 ' 20 .
We therefore checked the other choices of the axis
representation by the evaluation of s m . If the III r
axis representation is used, the denominator in
Eq. (9) has the largest value and a small s m seems
to be expected. However, for the unitary transformation which reduces R6 = 0 in the IIP axis representaTable IV.
(11)
sin = 2R5/(2Z-X-Y)
where
d
0.34875(10)
-8.563(3)
0.18028(8)
-75.07(6)
51479.4585(30)
5386.58814(25)
4868.99996(25)
9.81704
93.8212
103.7946
0.156408(7)
-41.9
0.324
Case 4
conditions a .
Case 5
6
0.34875(10)
-8.404(2)
0.16603(8)
-68.03(9)
51479.4586(30)
5386.58101(25)
4869.00701(25)
9.81704
93.8213
103.7945
0.156134(7)
-46.9
0.362
f
0.35753(4)
-8.484(2)
0.17320(5)
-75.97(4)
51479.4585(30)
5386.58460(25)
4869.00346(25)
9.81704
93.8212
103.7945
0.156272(7)
-44.4
0.343
MHz
kHz
MHz
kHz
MHz
MHz
MHz
amuA 2
amuA 2
amuA 2
amuA 2
MHz
Numbers in the parentheses are estimated errors on the basis of the standard error of the spectral constants in Table II.
In the case the error is not indicated the error is smaller than the last digit.
See text.
S The errors of the moment of inertia are limited by the uncertainty of the conversion factor, which was taken to be I
(amuA 2 ) = 5 1 0 5 3 7 6 x 1 0 5 / B ( M H z ) .
a
b _ f
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688
K. Yamada and M. Winnewisser • Centrifugal Distortion Constants of Vinyl Isocyanide 688
the nitrogen atom in the isocyanide group is much
f o r a radio astronomical search f o r this molecule.
smaller than that in the cyanides. For example, the
The relative magnitude of Einstein's A
value Xaa f o r methyl cyanide is — 4.35 MHz
which
f o r methyl isocyanide
23
and
represents
the probability
of
constant,
spontaneous
+ 0 . 4 8 8 5 M H z 2 4 . For ethyl
emission, f o r such transitions and line strengths f o r
and f o r ethyl isocyanide
all transitions listed in Table I are available f r o m
cyanide it is —3.3 MHz
25
the hyperfine splitting has not been observed. ThereVINYL ISOCYANIDE
fore, though the absolute value of Xaa is large in
vinyl cyanide,
—4.21
MHz2,
it is probably much
VINYLCYANIDE
Ii
+
5175 MHz
smaller f o r vinyl isocyanide. F r o m the absorption
T" ~ 4572 MHz
profile of the l o i ^ 0 0 < ) transitions we can estimate
the upper limit of the absolute value of Xaa f o r vinyl
isocyanide to be 0.5 MHz. Since we could not find
any hint of hyperfine structure in either q QK transitions or in 6-type transitions, it can be concluded
that the absolute value of
Xbb~Xcc
absorption
l 0 i — O 00 transition
profile
of
the
is small. The
2„
of
Y — NC is illustrated in Fig. 6 together with that of
vinyl cyanide f o r comparison. T h e hyperfine struc-
/
'
ture of V — NC estimated on the assumption Xaa —
+ 0.5 MHz and Xbb ~ Xcc
=
/
/
i-2 n
0.0 M H z is indicated in
the figure.
VINYL CYANIDE, H 2 O C H - C N
1 of
VINYL ISOCYANIDE, H 2 C=CH-NC
°oo
1QI~ OQO
Fig. 7. Part of the rotational energy level scheme of vinyl
isocyanide in the ground vibrational state as compared with
that of vinyl cyanide. The solid and dashed arrows indicate
a-type and b-type transitions respectively. The two heavy
arrows in the diagram for vinyl cyanide indicate two a-type
Q-branch transitions observed in Sgr B2.
the authors on request. The energy levels related to
the transitions listed in Table I are also shown in the
same table in c m - 1 unit.
9485
10253
Xbb~Xcc=0.0
d) Predictions
MHz.
of line
'
positions
Transitions of interest f r o m a radio-astronomical
point of view have been predicted and included in
Table I. Figure 7 shows a part of the rotational
energy level scheme of vinyl cyanide and vinyl isocyanide showing the possible transitions opportune
1
2
3
A
10255
Fig. 6. The absorption profile of the a-type lo,l -<— 0o,o
transition of vinyl isocyanide is compared with that of
vinyl cyanide. The hyperfine structures are indicated by the
line patterns showing the relative intensities. Those for
vinyl isocyanide were obtained assuming Xaa = 0.05 MHz and
F. F. Gardner and G. Winnewisser, Astrophys. J. Letters
195, L127 [1975].
M. C. L. Gerry and G. Winnewisser, J. Mol. Spectrosc.
48, 1 [1973].
G. Winnewisser, P. G. Mezger, and H. D. Breuer. Fortschritte der chemischen Forschung 44, 1 — 81 [1974].
cknowledgements
The authors would like to express their thanks to
Dr. Brenda P. Winnewisser f o r her help concerning
computer programming and discussions of the
manuscript. The assistance of the Max Planck Institut
für Radioastronomie through the grants of Dr. G.
Winnewisser in making the Hewlett-Packard M R R
spectrometer available is very much appreciated. The
authors also thank Dr. Gisbert Winnewisser f o r his
continuous interest in this work.
The calculations were made at the computer centers of the Universität Kiel and the Justus LiebigUniversität Giessen.
4
5
6
L. E. Snyder and D. Buhl. Bull. Amer. Astr. Soc. 3, 388
[1971].
K. Bolton, N. L. Owen, and J. Sheridan, Spectrochim.
Acta 26 A. 909 [1970].
J. K. G. Watson, J. Chem. Phys. 46. 1935 [1967] ; 48,
4517 [1968].
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K. Yamada and M. Winnewisser • Centrifugal Distortion Constants of Vinyl Isocyanide
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