|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
CF3(CF2)6CF2CN
|
 |
 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Nitrogen |
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
in n-Perfluorooctyl
Cyanide gauche-anti
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Calculation of the nitrogen nqcc's in n-perfluorooctyl 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. |
|
|
|
|
|
|
|
|
|
|
|
|
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. |
|
|
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). |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
Table 1. 14N nqcc's
in n-perfluorooctyl
cyanide, GA (MHz).
Calculation was made on ropt and ~ re structures
|
|
| |
|
|
|
|
|
|
|
|
|
|
|
ropt |
|
~ re |
|
Expt. |
|
| |
|
|
|
|
|
|
|
|
|
Xaa |
|
2.124 |
|
2.118 |
|
|
|
|
Xbb |
- |
4.525 |
- |
4.516 |
|
|
|
|
Xcc |
|
2.401 |
|
2.397 |
|
|
|
|
|Xab| |
|
1.134 * |
|
1.130 * |
|
|
|
|
|Xac| |
|
0.028 |
|
0.026 |
|
|
|
|
|Xbc| |
|
0.373 |
|
0.360 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
0.030 (1.3 %) |
|
0.030 (1.3 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
2.302 |
|
2.296 |
|
|
|
|
Xyy |
|
2.430 |
|
2.425 |
|
|
|
|
Xzz |
- |
4.732 |
- |
4.721 |
|
|
|
|
ETA |
|
0.0271 |
|
0.0272 |
|
|
|
|
Øz,CN |
|
0.32
|
|
0.32 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* The algebraic sign of the product XabXacXbc is
negative. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 2.
n-Perfluorooctyl Cyanide, GA.
Selected structure parameters, ropt and ~
re (Å and degrees). Complete
structures are given here in
Z-matrix format. |
| |
|
|
|
|
|
|
|
|
ropt |
|
~ re |
|
|
|
|
|
| C(1)C(2) |
|
1.5471 |
|
1.5458 |
| C(2)C(3) |
|
1.5506 |
|
1.5492 |
| C(3)C(4) |
|
1.5541 |
|
1.5525 |
| C(4)C(5) |
|
1.5546 |
|
1.5530 |
| C(5)C(6) |
|
1.5539 |
|
1.5523 |
| C(6)C(7) |
|
1.5504 |
|
1.5490 |
| C(7)C(8) |
|
1.5552 |
|
1.5536 |
| C(8)C(9) |
|
1.4758 |
|
1.4776 |
| C(9)N |
|
1.1534 |
|
1.1544 |
| C(1)C(2)C(3) |
|
113.88 |
|
113.88 |
| C(2)C(3)C(4) |
|
112.86 |
|
112.86 |
| C(3)C(4)C(5) |
|
112.76 |
|
112.76 |
| C(4)C(5)C(6) |
|
112.72 |
|
112.72 |
| C(5)C(6)C(7) |
|
112.97 |
|
112.97 |
| C(6)C(7)C(8) |
|
113.53 |
|
113.53 |
| C(7)C(8)C(9) |
|
113.14 |
|
113.14 |
| C(8)C(9)N |
|
178.67 |
|
178.67 |
| C(1)C(2)C(3)C(4) |
- |
163.27 |
- |
163.27 |
| C(2)C(3)C(4)C(5) |
- |
161.70 |
- |
161.70 |
| C(3)C(4)C(5)C(6) |
- |
161.91 |
- |
161.91 |
| C(4)C(5)C(6)C(7) |
- |
161.96 |
- |
161.96 |
| C(5)C(6)C(7)C(8) |
- |
161.82 |
- |
161.82 |
| C(6)C(7)C(8)C(9) |
|
74.14 |
|
74.14 |
|
C(7)C(8)C(9)N |
|
123.70 |
|
123.70 |
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
| Table 3.
n-Perfluorooctyl Cyanide, GA.
Rotational
Constants (MHz). |
|
|
|
|
|
|
|
ropt |
~ re |
Expt. |
|
|
|
|
|
|
A |
551.0 |
548.8 |
|
|
B |
94.6 |
94.7 |
|
|
C |
93.6 |
93.7 |
|
|
|
|
|
|
|
|µa| |
0.57 |
0.57 |
|
|
|µb| |
1.23 |
1.22 |
|
|
|µc| |
0.09 |
0.08 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Note: Etransoid <
EGA by 0.34 kJ/mol as calculated at the B3PW91/6-311+G(df)
level of theory on the B3P86/6-31G(2d) opt structures. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
n-Perfluorooctyl
Cyanide transoid |
n-Perfluorobutyl
Cyanide GA |
|
|
n-Perfluoropentyl
Cyanide GA |
n-Perfluorohexyl
Cyanide GA |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents |
|
|
|
|
|
Molecules/Nitrogen |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
C8F17CN_GA.html |
|
|
|
|
|
|
Last
Modified 23 June 2010 |
|
|
|
|
|
|
|
|
|
|