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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 transoid
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Calculation of the nitrogen nqcc's in n-perfluorohexyl
cyanide, transoid 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, transoid
(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 |
- |
2.163 |
- |
2.157 |
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Xbb |
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0.191 |
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0.187 |
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Xcc |
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1.972 |
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1.970 |
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|Xab| |
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3.203 * |
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3.197 * |
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|Xac| |
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1.254 |
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1.247 |
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|Xbc| |
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0.912 |
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0.910 |
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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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2.320 |
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2.316 |
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Xyy |
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2.435 |
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2.430 |
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Xzz |
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4.756 |
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4.745 |
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ETA |
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0.0240 |
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0.0240 |
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Øz,CN |
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0.39 |
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0.37 |
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* The algebraic sign of the product XabXacXbc is
negative. |
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| Table 2.
n-Perfluorohexyl Cyanide, transoid.
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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1.5473 |
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1.5460 |
| C(2)C(3) |
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1.5506 |
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1.5492 |
| C(3)C(4) |
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1.5541 |
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1.5525 |
| C(4)C(5) |
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1.5534 |
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1.5518 |
| C(5)C(6) |
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1.5523 |
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1.5508 |
| C(6)C(7) |
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1.4788 |
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1.4805 |
| 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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113.81 |
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113.81 |
| 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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112.63 |
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112.63 |
| C(4)C(5)C(6) |
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113.66 |
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113.66 |
| C(5)C(6)C(7) |
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110.12 |
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110.12 |
| C(6)C(7)N(8) |
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179.46 |
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179.46 |
| C(1)C(2)C(3)C(4) |
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163.19 |
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163.19 |
| C(2)C(3)C(4)C(5) |
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161.86 |
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161.86 |
| C(3)C(4)C(5)C(6) |
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162.22 |
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162.22 |
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C(4)C(5)C(6)C(7) |
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168.46 |
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168.46 |
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C(5)C(6)C(7)N(8) |
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65.95 |
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65.95 |
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| Table 3.
n-Perfluorohexyl Cyanide, transoid.
Rotational
Constants (MHz) and Dipole Moments (D). |
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ropt |
~ re |
Expt. |
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A |
794.3 |
791.0 |
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B |
184.0 |
184.1 |
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C |
179.8 |
180.0 |
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|µa| |
1.26 |
1.24 |
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|µb| |
0.69 |
0.68 |
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|µc| |
0.34 |
0.33 |
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Note: Etransoid <
EGA by about 0.40 kJ/mol, as calculated at the
B3PW91/6-311+G(df) level of theory on the B3P86/6-31G(2d) opt
structures. |
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A frequency calculation on the all trans (Cs)
conformer at the B3P86/6-31G(2d) level of
theory gives two
imaginary frequencies. Thus, this conformer is NOT an energy
minimum, nor is it 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, GA |
n-Perfluorobutyl
Cyanide, transoid |
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n-Perfluoropentyl
Cyanide, transoid |
n-Perfluoroheptyl
Cyanide, transoid |
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Table of Contents |
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Molecules/Nitrogen |
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C6F13CN_transoid.html |
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Last
Modified 3 June 2010 |
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