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C6H5-CHCH-CN
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Nitrogen
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Nuclear
Quadrupole Coupling Constants |
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in Phenylvinylnitrile |
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Calculation of the N nqcc tensors in Z- and E-phenylvinylnitrile was
made here on molecular structures of optimized at the B3P86/6-31G(3d,3p) level of
theory. These nqcc's are compared with the experimental values [1]
in Tables 1 and 2. Rotational
constants are given in Table 3. |
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Z |
E |
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In Tables 1 and 2, subscripts a,b,c
refer to
the principal axes of the inertia tensor, subscripts x,y,z to the
principal axes of the nqcc tensor. ETA = (Xxx - Xyy)/Xzz.
Ø (degrees) is the angle between its subscripted
parameters.
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RMS is the root mean square
difference between calculated and experimental diagonal nqcc's
(percentage of the average of the magnitudes of the experimental
nqcc's). RSD is
the residual standard deviation of the B3PW91/6-311+G(df,pd) model for
calculation of the coupling constants. |
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Table 1. 14N nqcc's in Z-Phenylvinylnitrile
(MHz).
Calculation was made
on the B3P86/6-31G(3d,3p) opt structure. |
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Calc |
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Expt [1] |
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14N |
Xaa |
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1.087 |
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1.147(30) |
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Xbb - Xcc |
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5.177
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5.291(12)
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Xbb |
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3.132 |
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3.219(16) *
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Xcc |
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2.045 |
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2.072(16) *
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|Xab| |
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2.343 |
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RMS
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0.063 (2.9 %)
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RSD |
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0.030 (1.3 %) |
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Xxx |
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2.130 |
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Xyy |
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2.045 |
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Xzz |
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4.175 |
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ETA |
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0.0204 |
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Øz,a |
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66.00 |
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Øa,CN |
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64.90
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Øz,CN |
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1.10
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* Derived here from experimental Xaa and Xbb - Xcc.
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Table 2. 14N nqcc's in E-Phenylvinylnitrile
(MHz).
Calculation was made
on the B3P86/6-31G(3d,3p) opt structure. |
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Calc |
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Expt [1] |
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14N |
Xaa |
-
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3.766 |
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3.839(123) |
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Xbb - Xcc |
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0.030
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-
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0.192(4)
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Xbb |
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1.868 |
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1.824(61) *
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Xcc |
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1.898 |
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2.015(61) *
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|Xab| |
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1.585 |
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RMS
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0.084 (3.3 %)
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RSD |
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0.030 (1.3 %) |
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Xxx |
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2.283 |
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Xyy |
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1.898 |
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Xzz |
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4.181 |
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ETA |
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0.0920 |
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Øz,a |
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14.68 |
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Øa,CN |
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14.08
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Øz,CN |
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0.60
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* Derived here from experimental Xaa and Xbb - Xcc.
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| Table 3. Phenylvinylnitrile.
Rotational Constants (MHz). Calc is
on the
B3P86/6-31G(3d,3p) opt structure. |
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_____________Z_______________ |
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Calc |
Expt [1] |
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A |
3169.9 |
3122.8826(13) |
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B |
870.4
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873.25109(62) |
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C |
682.9
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683.73089(43) |
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_______________E_________________ |
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A |
5144.9 |
5102.4108(20) |
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B |
609.6
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607.51435(69) |
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C |
545.0
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543.21036(62) |
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[1]
A.O.Hernandez-Castillo, C.Abeysekera, B.M.Hays , and
T.S.Zwier, J.Chem.Phys. 145,114203(2016). NOTE: The expt nqcc's
given in Tables 1 and 2 differ from those given in this paper.
These have been corrected and obtained by private communication with
T.S.Zwier.
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Benzonitrile
|
Vinylnitrile
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Benzyl Cyanide
| Ethyl Cyanide
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Table of Contents |
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Molecules/Nitrogen |
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PVN.html |
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Last
Modified 28 Sept 2016 |
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