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CF3(CF2)4CF2CN
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Nitrogen |
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Nuclear
Quadrupole Coupling Constants |
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in n-Perfluorohexyl
Cyanide gauche-anti
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Calculation of the nitrogen nqcc's in n-perfluorohexyl
cyanide, GA was made on structures given by
B3P86/6-31G(2d) optimization (ropt), and on this same
structure but with empirically derived
equilibrium CF, C-C, and CN bond lengths
(~ re).
These calculated nqcc's are given in Table 1. Structure
parameters are
given in
Table 2, rotational constants and dipole moments in Table 3. |
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In Table 1,
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 principal z-axis of the nqcc tensor and the CN bond
axis. ETA = (Xxx - Xyy)/Xzz. |
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RSD is the calibration residual
standard deviation of
the B3PW91/6-311+G(df,pd) model for calculation of the nitrogen nqcc's,
which may be taken as an estimate of the uncertainty in the calculated
nqcc's (unertainties in the structures not-with-standing). |
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Table 1. 14N nqcc's in
n-Perfluorohexyl Cyanide, GA (MHz).
Calculation was made on ropt and ~ re structures
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ropt |
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~ re |
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Expt. |
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Xaa |
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2.046 |
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2.041 |
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Xbb |
- |
4.310 |
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4.304 |
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Xcc |
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2.264 |
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2.263 |
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|Xab| |
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1.326 * |
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1.322 * |
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|Xac| |
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0.239 |
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0.236 |
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|Xbc| |
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1.022 |
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1.009 |
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RSD |
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0.030 (1.3 %) |
0.030 (1.3 %) |
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Xxx |
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2.302 |
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2.296 |
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Xyy |
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2.431 |
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2.425 |
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Xzz |
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4.733 |
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4.722 |
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ETA |
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0.0272 |
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0.0273 |
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Øz,CN |
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0.31 |
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0.31 |
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* The algebraic sign of the product XabXacXbc is
negative. |
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| Table 2.
n-Perfluorohexyl Cyanide, GA.
Selected structure parameters, ropt and ~
re (Å and degrees). Complete
structures are given here in
Z-matrix format. |
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ropt |
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~ re |
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| C(1)C(2) |
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1.5472 |
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1.5459 |
| C(2)C(3) |
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1.5504 |
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1.5490 |
| C(3)C(4) |
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1.5529 |
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1.5514 |
| C(4)C(5) |
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1.5501 |
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1.5486 |
| C(5)C(6) |
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1.5552 |
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1.5536 |
| C(6)C(7) |
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1.4758 |
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1.4776 |
| C(7)N(8) |
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1.1534 |
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1.1544 |
| C(1)C(2)C(3) |
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113.83 |
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113.83 |
| C(2)C(3)C(4) |
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112.92 |
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112.92 |
| C(3)C(4)C(5) |
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113.03 |
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113.03 |
| C(4)C(5)C(6) |
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113.59 |
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113.59 |
| C(5)C(6)C(7) |
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113.18 |
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113.18 |
| C(6)C(7)N(8) |
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178.67 |
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178.67 |
| C(1)C(2)C(3)C(4) |
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163.30 |
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163.30 |
| C(2)C(3)C(4)C(5) |
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162.30 |
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162.30 |
| C(3)C(4)C(5)C(6) |
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162.13 |
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162.13 |
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C(4)C(5)C(6)C(7) |
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74.01 |
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74.01 |
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C(5)C(6)C(7)N(8) |
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124.64 |
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124.64 |
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| Table 3.
n-Perfluorohexyl Cyanide, GA. Rotational
Constants (MHz) and Dipole Moments (D). |
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ropt |
~ re |
Expt. |
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A |
718.2 |
715.4 |
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B |
192.2 |
192.3 |
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C |
188.9 |
189.0 |
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|µa| |
0.59 |
0.59 |
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|µb| |
1.23 |
1.22 |
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|µc| |
0.15 |
0.15 |
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For the all trans (Cs)
conformer, the structure was optimized at the B3P86/6-31G(2d) level of
theory. A frequency calculation on this structure gives two
imaginary frequencies. Thus, this structure is a second-order
saddle point. It is NOT an energy minimum. It is NOT a
transition structure that connects two minima [1]. |
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[1] J.B.Foresman and AE.Frisch,
Exploring Chemistry with Electronic Structure Methods, 2nd ed.,
Gaussian, Inc. Pittsburgh, PA 1995-96. |
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n-Perfluorohexyl
Cyanide, transoid |
n-Perfluorobutyl
Cyanide, GA |
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n-Perfluoropentyl
Cyanide, GA |
n-Perfluoroheptyl
Cyanide, GA |
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Table of Contents |
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Molecules/Nitrogen |
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C6F13CN_GA.html |
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Last
Modified 3 June 2010 |
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