|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
CH3CH2CH2CH2CN
|
 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Nitrogen
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
|
in
n-Butyl Cyanide anti-anti |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Calculations of the nitrogen nqcc's
in the anti-anti conformer of n-butyl cyanide were made on
molecular structures derived by (1)
MP2/6-311+G(d,p) and (2) MP2/6-311+G(2d,p) optimization each with
empirically corrected approximate equilibrium bond lengths; by (3) MP2/6-311+G(3df,3pd) optimization with
empirically corrected approximate equilibrium bond lengths, and (4) MP2/aug-cc-pVTZ optimization with
empirically corrected approximate equilibrium bond lengths. These
nqcc's are
compared in Tables 1 and 2 with the experimental values of Bohn, et al.
[1].
Structure parameters are given in Table 3, rotational constants
in Table 4. |
|
|
|
|
|
|
|
|
|
|
|
|
In Tables 1 and 2, subscripts a,b,c
refer to principal axes of the inertia tensor, subscripts x,y,z to
principal axes of the nqcc tensor. The nqcc y-axis is chosen
coincident with the inertia c-axis, these are perpendicular to the Cs
plane of the molecule. Ø (degrees) is the angle between
its subscripted parameters. ETA = (Xxx - Xyy)/Xzz. |
|
|
RMS is the root mean square
difference between calculated and experimental nqcc's (percentage of
average experimental nqcc). RSD is the residual standard
deviation
of calibration of the B3PW91/6-311+G(df,pd) model for calculation of
the nqcc's. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
Table 1. 14N nqcc's in n-Butyl
Cyanide, anti-anti (MHz).
Calculation was made on structures (1) MP2/6-311+G(d,p)
and (2) MP2/6-311+G(2d,p), each with approximate equilibrium bond
lengths. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc (1)
|
|
Calc (2) |
|
Expt. [1] |
|
| |
|
|
|
|
|
|
|
|
|
Xaa |
- |
2.709 |
- |
2.728 |
- |
2.726(2) |
|
|
Xbb |
|
0.642 |
|
0.663 |
|
0.674(2) |
|
|
Xcc |
|
2.067 |
|
2.065 |
|
2.050(3) |
|
|
|Xab| |
|
2.689 |
|
2.678 |
|
2.678(30) * |
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
0.023 (1.2 %) |
|
0.011 (0.60 %) |
|
|
|
|
RSD |
|
0.030 (1.3 %) |
|
0.030 (1.3 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
2.135 |
|
2.137 |
|
2.146(25) ** |
|
|
Xyy |
|
2.067 |
|
2.065 |
|
2.050(3) |
|
|
Xzz |
- |
4.202 |
- |
4.202 |
- |
4.198(25) |
|
|
ETA |
- |
0.016 |
- |
0.017 |
- |
0.023(6) |
|
|
Øz,a |
|
29.03 |
|
28.83 |
|
28.80(14) |
|
|
Øa,CN |
|
29.38 |
|
29.07 |
|
|
|
|
Øz,CN |
|
0.35 |
|
0.24 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
|
* Calc (2) value. Uncertainity
assumed to be 1*RSD. |
|
|
** Calculated here using Kisiel's
QDIAG.f program. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
Table 2. 14N nqcc's in n-Butyl
Cyanide, anti-anti (MHz).
Calculation was made on structures (3) MP2/6-311+G(3df,3pd) and
(4) MP2/aug-cc-pVTZ, each with approximate equilibrium bond lengths. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc (3)
|
|
Calc (4) |
|
Expt. [1] |
|
| |
|
|
|
|
|
|
|
|
|
Xaa |
- |
2.701 |
- |
2.711 |
- |
2.726(2) |
|
|
Xbb |
|
0.630 |
|
0.640 |
|
0.674(2) |
|
|
Xcc |
|
2.071 |
|
2.070 |
|
2.050(3) |
|
|
|Xab| |
|
2.694 |
|
2.689 |
|
2.689(30) * |
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
0.031 (1.7 %) |
|
0.024 (1.3 %) |
|
|
|
|
RSD |
|
0.030 (1.3 %) |
|
0.030 (1.3 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
2.131 |
|
2.133 |
|
2.155(25) ** |
|
|
Xyy |
|
2.071 |
|
2.070 |
|
2.050(3) |
|
|
Xzz |
- |
4.203 |
- |
4.204 |
- |
4.207(25) |
|
|
ETA |
- |
0.014 |
- |
0.015 |
- |
0.025(6) |
|
|
Øz,a |
|
29.13 |
|
29.04 |
|
28.85(14) |
|
|
Øa,CN |
|
29.49 |
|
29.38 |
|
|
|
|
Øz,CN |
|
0.36 |
|
0.34 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* Calc (4) value. Uncertainity
assumed to be 1*RSD.
|
|
|
** Calculated here using Kisiel's
QDIAG.f program. |
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
| Table 3. n-Butyl Cyanide,
anti-anti.
Heavy atom molecular structure parameters (Å and degrees).
Complete structures are given here
in Z-matrix format. |
| |
|
|
|
|
|
|
|
(1) |
(2) |
(3) |
(4) |
 |
|
|
|
|
|
| NC(2) |
1.1563 |
1.1563 |
1.1562 |
1.1561 |
| C(2)C(3) |
1.4612 |
1.4612 |
1.4604 |
1.4600 |
| C(3)C(4) |
1.5278 |
1.5278 |
1.5281 |
1.5278 |
| C(4)C(5) |
1.5202 |
1.5202 |
1.5198 |
1.5202 |
| C(5)C(6) |
1.5208 |
1.5208 |
1.5206 |
1.5208 |
| NC(2)C(3) |
178.48 |
178.70 |
178.38 |
178.43 |
| C(2)C(3)C(4) |
112.13 |
112.18 |
111.95 |
112.02 |
| C(3)C(4)C(5) |
111.90 |
111.67 |
111.58 |
111.51 |
| C(4)C(5)C(6) |
112.16 |
112.12 |
111.97 |
111.96 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
| Table 4.
n-Butyl Cyanide, anti-anti.
Rotational Constants (MHz). |
|
|
|
|
|
|
|
(1) |
(2) |
(3) |
(4) |
Expt. [1] |
|
|
|
|
|
|
| A |
15078.8 |
15140.1 |
15070.7 |
15095.8 |
15028.4681(10) |
| B |
1345.3 |
1344.6 |
1349.0 |
1348.5 |
1334.1061(3) |
| C |
1274.0 |
1273.7 |
1277.1 |
1276.8 |
1263.8578(3) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
[1] R.K.Bohn, J.L.Pardus,
J.August, T.Brupbacher, and
W.Jäger, J.Mol.Struct. 413-414,293(1997). |
|
|
|
|
|
|
|
|
|
|
|
|
M.H.Ordu, H.S.P.Müller, A.Walters, M.Nuñez, F.Lewen, A.Belloche, K.M.Menton, and S.Schlemmer, A&A, 541,A121(2012): Xaa = -2.7267(16), Xbb = 0.6753(17), Xcc = 2.0514(20) MHz
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
n-Butyl Cyanide, anti-gauche |
CH3CN |
|
|
|
n-Butyl
Cyanide, gauche-anti |
CH3CH2CN |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents |
|
|
|
|
|
Molecules/Nitrogen |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
butylCN_aa.html |
|
|
|
|
|
|
Last
Modified 6 June 2017 |
|
|
|
|
|
|
|
|
|
|