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CF3(CF2)5CF2CN
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Nitrogen |
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Nuclear
Quadrupole Coupling Constants |
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in n-Perfluoroheptyl
Cyanide transoid
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(Perfluorooctanonitrile)
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Calculation of the nitrogen nqcc's in n-perfluoroheptyl 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-perfluoroheptyl
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. [1] ** |
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Xaa |
- |
2.226 |
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2.220 |
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Xbb |
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0.553 |
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0.547 |
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Xcc |
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1.673 |
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1.673 |
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|Xab| |
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2.956 * |
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2.951 * |
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|Xac| |
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1.717 |
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1.709 |
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|Xbc| |
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1.119 |
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1.117 |
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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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2.321 |
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2.316 |
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Xyy |
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2.434 |
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2.429 |
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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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0.0238 |
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0.0238 |
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Øz,CN |
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0.39 |
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0.38 |
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* The algebraic sign of the product XabXacXbc is
negative. |
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** "Nitrogen hyperfine splitting was
not resolvable ..." [1] |
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| Table 2.
n-Perfluoroheptyl 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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1.5471 |
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1.5458 |
| C(2)C(3) |
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1.5507 |
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1.5492 |
| C(3)C(4) |
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1.5544 |
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1.5528 |
| C(4)C(5) |
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1.5551 |
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1.5534 |
| C(5)C(6) |
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1.5534 |
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1.5518 |
| C(6)C(7) |
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1.5528 |
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1.5508 |
| C(7)C(8) |
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1.4789 |
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1.4805 |
| C(8)N(9) |
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1.1534 |
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1.1544 |
| C(1)C(2)C(3) |
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113.88 |
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113.88 |
| C(2)C(3)C(4) |
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112.89 |
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112.89 |
| C(3)C(4)C(5) |
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112.72 |
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112.72 |
| C(4)C(5)C(6) |
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112.60 |
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112.60 |
| C(5)C(6)C(7) |
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113.68 |
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113.68 |
| C(6)C(7)C(8) |
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110.09 |
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110.09 |
| C(7)C(8)N(9) |
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179.47 |
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179.47 |
| C(1)C(2)C(3)C(4) |
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163.37 |
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163.37 |
| C(2)C(3)C(4)C(5) |
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161.78 |
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161.78 |
| C(3)C(4)C(5)C(6) |
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161.78 |
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161.78 |
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C(4)C(5)C(6)C(7) |
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162.58 |
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162.58 |
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C(5)C(6)C(7)C(8) |
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168.77 |
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168.77 |
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C(6)C(7)C(8)N(9) |
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64.92 |
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64.92 |
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| Table 3.
n-Perfluoroheptyl Cyanide, transoid.
Rotational
Constants (MHz). |
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ropt |
~ re |
Expt. [1] |
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A |
684.1 |
681.2 |
681.37155(18) |
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B |
127.2 |
127.4 |
126.116097(48) |
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C |
125.5 |
125.6 |
124.284824(49) |
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|µa| |
1.28 |
1.26 |
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|µb| |
0.70 |
0.69 |
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|µc| |
0.36 |
0.35 |
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Note: Etransoid <
EGA by 0.47 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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[1] W.C.Bailey, R.K.Bohn,
C.T.Dewberry, G.S.Grubbs II, and S.A.Cooke, J.Mol.Spectrosc. 270,61(2011). "Nitrogen hyperfine splitting was not
resolvable ..." |
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n-Perfluoroheptyl
Cyanide GA |
n-Perfluorobutyl
Cyanide transoid |
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n-Perfluoropentyl
Cyanide transoid |
n-Perfluorohexyl
Cyanide transoid |
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Table of Contents |
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Molecules/Nitrogen |
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C7F15CN_transoid.html |
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Last
Modified 4 June 2010 |
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