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CH3CH2CH2CH2CN
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Nitrogen
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Nuclear
Quadrupole Coupling Constants |
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in
n-Butyl Cyanide gauche-anti |
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Calculations of the nitrogen nqcc's
in the gauche-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. |
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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. Øz,CN
(degrees) is the angle between the z-principal axis and the CN bond
direction. ETA = (Xxx - Xyy)/Xzz. |
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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. |
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Table 1. 14N nqcc's in n-Butyl
Cyanide, gauche-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 MP2/6-311+G(d,p)
equilibrium bond
lengths. |
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Calc (1)
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Calc (2) |
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Expt. [1] |
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Xaa |
- |
0.020 |
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0.050 |
- |
0.042(2) |
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Xbb |
- |
1.954 |
- |
1.923 |
- |
1.935(2) |
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Xcc |
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1.974 |
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1.973 |
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1.977(3) |
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|Xab| |
- |
2.956 |
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2.968 |
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2.968(30) * |
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|Xac| |
- |
0.509 |
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0.512 |
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0.512(30) * |
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|Xbc| |
- |
0.614 |
- |
0.607 |
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0.607(30) * |
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RMS |
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0.017 (1.3 %) |
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0.008 (0.65 %) |
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RSD |
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0.030 (1.3 %) |
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0.030 (1.3 %) |
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Xxx |
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2.157 |
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2.160 |
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2.162(33) |
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Xyy |
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2.043 |
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2.041 |
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2.043(29) |
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Xzz |
- |
4.200 |
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4.201 |
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4.205(29) |
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ETA |
- |
0.027 |
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0.028 |
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0.028 |
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Øz,CN |
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0.29 |
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0.23 |
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* Calc (2) value. Uncertainity
arbitrarily assumed to be 1*RSD. |
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** Calculated here using Kisiel's
QDIAG.f program. |
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Table 2. 14N nqcc's in n-Butyl
Cyanide, gauche-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. |
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Calc (3)
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Calc (4) |
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Expt. [1] |
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Xaa |
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0.027 |
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0.041 |
- |
0.042(2) |
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Xbb |
- |
2.003 |
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2.018 |
- |
1.935(2) |
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Xcc |
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1.976 |
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1.977 |
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1.977(3) |
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|Xab| |
- |
2.943 |
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2.940 |
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|Xac| |
- |
0.496 |
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0.492 |
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|Xbc| |
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0.609 |
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0.607 |
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RMS |
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0.056 (4.2 %) |
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0.068 (5.2 %) |
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RSD |
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0.030 (1.3 %) |
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0.030 (1.3 %) |
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Xxx |
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2.156 |
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2.157 |
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Xyy |
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2.045 |
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2.045 |
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Xzz |
- |
4.201 |
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4.202 |
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ETA |
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0.026 |
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0.027 |
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Øz,CN |
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0.39 |
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0.41 |
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* Calc (4) value. Uncertainity
arbitrarily assumed to be 1*RMS.
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** Calculated here using Kisiel's
QDIAG.f program. |
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| Table 3. n-Butyl
Cyanide, gauche-anti.
Heavy atom molecular structure parameters (Å and degrees).
Complete structures are given here
in Z-matrix format. |
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(1) |
(2) |
(3) |
(4) |
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| NC(2) |
1.1564 |
1.1564 |
1.1563 |
1.1562 |
| C(2)C(3) |
1.4624 |
1.4624 |
1.4615 |
1.4612 |
| C(3)C(6) |
1.5289 |
1.5289 |
1.5293 |
1.5294 |
| C(6)C(7) |
1.5200 |
1.5200 |
1.5197 |
1.5202 |
| C(7)C(8) |
1.5208 |
1.5208 |
1.5206 |
1.5210 |
| NC(2)C(3) |
178.62 |
178.81 |
178.36 |
178.34 |
| C(2)C(3)C(6) |
111.77 |
112.01 |
111.53 |
111.53 |
| C(3)C(6)C(7) |
113.00 |
113.23 |
112.82 |
112.80 |
| C(6)C(7)C(8) |
112.14 |
112.27 |
111.87 |
111.86 |
| C(7)C(6)C(3)C(2) |
- 61.07 |
- 60.88 |
- 61.91 |
- 61.68 |
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| Table 4.
n-Butyl Cyanide, gauche-anti.
Rotational Constants (MHz). |
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Calc (1) |
Calc (2) |
Calc (3) |
Calc (4) |
Expt. [1] |
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| A |
7671.4 |
7706.0 |
7609.7 |
7587.9 |
7635.6210(20) |
| B |
1813.9 |
1805.0 |
1825.1 |
1828.2 |
1788.6327(3) |
| C |
1572.2 |
1566.2 |
1580.5 |
1581.9 |
1554.2213(3) |
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[1] R.K.Bohn, J.L.Pardus,
J.August, T.Brupbacher, and
W.Jäger, J.Mol.Struct. 413-414,293(1997). |
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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 = -0.0413(21), Xbb = -1.9351(18), Xcc = 1.9764(16) MHz |
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n-Butyl Cyanide, anti-anti |
CH3CN |
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n-Butyl
Cyanide, anti-gauche |
CH3CH2CN |
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Table of Contents |
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Molecules/Nitrogen |
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butylCN_ga.html |
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Last
Modified 6 June 2017 |
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