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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 anti-gauche |
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Calculations of the nitrogen nqcc's
in the anti-gauche 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, anti-gauche (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 |
- |
3.709 |
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3.692 |
- |
3.645(3) |
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Xbb |
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1.943 |
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1.961 |
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1.988(3) |
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Xcc |
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1.766 |
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1.730 |
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1.657(4) |
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|Xab| |
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0.938 |
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0.875 |
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|Xac| |
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1.405 |
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1.476 |
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|Xbc| |
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0.189 |
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1.730 |
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RMS |
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0.078 (3.2 %) |
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0.053 (2.2 %) |
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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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2.136 |
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2.137 |
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Xyy |
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2.062 |
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2.061 |
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Xzz |
- |
4.197 |
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4.197 |
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ETA |
- |
0.018 |
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0.018 |
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Øz,CN |
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0.38 |
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0.24 |
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Table 2. 14N nqcc's in n-Butyl
Cyanide, anti-gauche (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 |
- |
3.667 |
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3.670 |
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3.645(3) |
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Xbb |
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1.960 |
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1.961 |
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1.988(3) |
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Xcc |
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1.707 |
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1.708 |
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1.657(4) |
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|Xab| |
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0.864 |
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0.867 |
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0.867(36) * |
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|Xac| |
- |
1.524 |
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1.522 |
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1.522(36) * |
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|Xbc| |
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0.195 |
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0.194 |
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0.194(36) * |
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RMS |
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0.035 (1.4 %) |
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0.036 (1.5 %) |
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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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2.132 |
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2.133 |
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2.134(30) ** |
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Xyy |
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2.064 |
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2.065 |
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2.045(30) |
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Xzz |
- |
4.196 |
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4.198 |
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4.179(20) |
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ETA |
- |
0.016 |
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0.016 |
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0.021(10) |
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Øz,CN |
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0.34 |
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0.39 |
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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,
anti-gauche.
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) |
1.1562 |
1.1562 |
1.1563 |
1.1561 |
| C(2)C(3) |
1.4610 |
1.4610 |
1.4602 |
1.4597 |
| C(3)C(6) |
1.5294 |
1.5294 |
1.5297 |
1.5298 |
| C(6)C(7) |
1.5228 |
1.5228 |
1.5227 |
1.5232 |
| C(7)C(8) |
1.5208 |
1.5208 |
1.5220 |
1.5226 |
| NC(2)C(3) |
178.45 |
178.75 |
178.44 |
178.35 |
| C(2)C(3)C(6) |
111.76 |
111.79 |
111.55 |
111.58 |
| C(3)C(6)C(7) |
112.55 |
112.47 |
112.28 |
112.24 |
| C(6)C(7)C(8) |
113.61 |
113.68 |
113.49 |
113.46 |
| C(3)C(6)C(7)C(8) |
62.04 |
63.18 |
63.47 |
63.50 |
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| Table 4.
n-Butyl Cyanide, anti-gauche.
Rotational Constants (MHz). |
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Calc (1) |
Calc (2) |
Calc (3) |
Calc (4) |
Expt. [1] |
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| A |
12100.8 |
12058.7 |
12007.4 |
11999.4 |
11887.4659(17) |
| B |
1505.2 |
1502.8 |
1508.2 |
1508.3 |
1486.1854(5) |
| C |
1427.5 |
1427.6 |
1433.3 |
1433.3 |
1415.7621(5) |
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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 = -3.6437(22), Xbb = 1.9877(21), Xcc = 1.6560(19) MHz
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n-Butyl Cyanide, anti-anti |
CH3CN |
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n-Butyl
Cyanide, gauche-anti |
CH3CH2CN |
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Table of Contents |
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Molecules/Nitrogen |
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butylCN_ag.html |
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Last
Modified 6 June 2017 |
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