CF3(CF2)4CF2CN




 
 
 


Nitrogen


Nuclear Quadrupole Coupling Constants

in n-Perfluorohexyl Cyanide gauche-anti


 







 
 
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.
 
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-Perfluorohexyl Cyanide, GA (MHz).  Calculation was made on ropt and ~ re structures
   





 ropt  ~ re Expt.
   




Xaa 2.046 2.041
Xbb - 4.310 - 4.304
Xcc 2.264 2.263
|Xab| 1.326 * 1.322 *
|Xac| 0.239 0.236
|Xbc| 1.022 1.009
 
RSD 0.030 (1.3 %) 0.030 (1.3 %)
 
Xxx 2.302 2.296
Xyy 2.431 2.425
Xzz - 4.733 - 4.722
ETA 0.0272 0.0273
Øz,CN 0.31 0.31
 

 
* The algebraic sign of the product XabXacXbc is negative.
 
 
Table 2.  n-Perfluorohexyl 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) 1.5472 1.5459
C(2)C(3) 1.5504 1.5490
C(3)C(4) 1.5529 1.5514
C(4)C(5) 1.5501 1.5486
C(5)C(6) 1.5552 1.5536
C(6)C(7) 1.4758 1.4776
C(7)N(8) 1.1534 1.1544
C(1)C(2)C(3) 113.83 113.83
C(2)C(3)C(4) 112.92 112.92
C(3)C(4)C(5) 113.03 113.03
C(4)C(5)C(6) 113.59 113.59
C(5)C(6)C(7) 113.18 113.18
C(6)C(7)N(8) 178.67 178.67
C(1)C(2)C(3)C(4) - 163.30 - 163.30
C(2)C(3)C(4)C(5) - 162.30 - 162.30
C(3)C(4)C(5)C(6) - 162.13 - 162.13
C(4)C(5)C(6)C(7)   74.01   74.01
C(5)C(6)C(7)N(8) 124.64 124.64

 
 
Table 3.  n-Perfluorohexyl Cyanide, GA.  Rotational Constants (MHz) and Dipole Moments (D).
 ropt  ~ re  Expt.
A 718.2 715.4
B 192.2 192.3
C 188.9 189.0
 
a| 0.59 0.59
b| 1.23 1.22
c| 0.15 0.15

 
 
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].
 
 
[1] J.B.Foresman and AE.Frisch, Exploring Chemistry with Electronic Structure Methods, 2nd ed., Gaussian, Inc. Pittsburgh, PA 1995-96.
 
 
n-Perfluorohexyl Cyanide, transoid n-Perfluorobutyl Cyanide, GA
n-Perfluoropentyl Cyanide, GA n-Perfluoroheptyl Cyanide, GA
 

 








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Last Modified 3 June 2010