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CF3(CF2)3CF2CN
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Nitrogen |
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Nuclear
Quadrupole Coupling Constants |
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in n-Perfluoropentyl
gauche-anti
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Calculation of the nitrogen nqcc's in n-perfluoropentyl 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 electric 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-perfluoropentyl
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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1.847 |
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1.843 |
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Xbb |
- |
3.471 |
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3.478 |
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Xcc |
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1.624 |
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1.635 |
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|Xab| |
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1.629 * |
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1.627 * |
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|Xac| |
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0.632 |
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0.624 |
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|Xbc| |
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2.169 |
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2.148 |
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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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2.304 |
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2.298 |
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Xyy |
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2.430 |
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2.424 |
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Xzz |
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4.734 |
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4.723 |
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ETA |
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0.0266 |
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0.0267 |
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Øz,CN |
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0.31 |
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0.30 |
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* The algebraic sign of the product XabXacXbc is
negative. |
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| Table 2.
n-Perfluoropentyl 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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1.5469 |
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1.5456 |
| C(2)C(3) |
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1.5493 |
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1.5479 |
| C(3)C(4) |
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1.5495 |
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1.5581 |
| C(4)C(5) |
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1.5549 |
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1.5533 |
| C(5)C(6) |
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1.4758 |
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1.4776 |
| C(6)N(7) |
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1.1534 |
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1.1544 |
| C(1)C(2)C(3) |
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113.97 |
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113.97 |
| C(2)C(3)C(4) |
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113.13 |
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113.13 |
| C(3)C(4)C(5) |
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113.65 |
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113.65 |
| C(4)C(5)C(6) |
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113.15 |
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113.15 |
| C(5)C(6)N(7) |
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178.70 |
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178.70 |
| C(1)C(2)C(3)C(4) |
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163.89 |
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163.89 |
| C(2)C(3)C(4)C(5) |
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162.00 |
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162.00 |
| C(3)C(4)C(5)C(6) |
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73.93 |
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73.93 |
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C(4)C(5)C(6)N(7) |
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124.95 |
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124.95 |
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| Table 3.
n-Perfluoropentyl Cyanide, GA. Rotational
Constants (MHz) and Dipole Moments (D). |
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ropt |
~ re |
Expt. |
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A |
849.4 |
846.1 |
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B |
293.7 |
293.8 |
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C |
285.3 |
285.4 |
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|µa| |
0.65 |
0.65 |
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|µb| |
1.16 |
1.14 |
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|µc| |
0.49 |
0.49 |
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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 one
imaginary frequency. It is, therefore, 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-Perfluoropentyl
Cyanide transoid |
n-Perfluorobutyl
Cyanide
GA |
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n-Perfluorohexyl
GA |
n-Perfluoroheptyl
Cyanide GA |
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Table of Contents |
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Molecules/Nitrogen |
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C5F11CN_GA.html |
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Last
Modified 27 May 2010 |
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