CH2F-CH2CN







 








 








Nitrogen

Nuclear Quadrupole Coupling Constants


in 3-Fluoropropionitrile


 








 








Calculations of the N nqcc tensors in 3-fluoropropionitrile, antiperiplanar and synclinal, were made on a molecular structures derived by MP2/aug-cc-pVTZ(G03) optimization with empirical correction of the  CC, CN, and CF bond lengths, re(1); and by MP2/6-311+G(3df,3pd) optimization also with empirical correction of the  CC, CN, and CF bond lengths, re(2).  These nqcc's are given in Tables 1 and 2.  Structure parameters are given in Table 3, rotational constants in Table 4.












antiperiplanar

synclinal






















































In Tables 1 and 2, subscripts a,b,c refer to the principal axes of the inertia tensor, subscripts x,y,z to the principal axes of the nqcc tensor.  ETA = (Xxx - Xyy)/Xzz,  Ø (degrees) is the angle between its subscripted parameters.

RSD is the residual standard deviation of calibration of the B3PW91/6-311+G(df,pd) model for calculation of the nitrogen nqcc's.

 








 








   








Table 1. Nitrogen nqcc's in antiperiplanar 3-Fluoropropionitrile (MHz).  Calculation was made on approximate equilibrium re(1) and re(2) structures.
   











Calc / re(1)
Calc / re(2)
Expt.
   








14N Xaa -
 3.416
 -
 3.417




Xbb
1.374
1.375




Xcc
2.042
2.043




|Xab|
2.245
2.242



 









RSD
0.030 (1.3 %)
0.030 (1.3 %)



 









Xxx
2.261
2.260




Xyy
2.042
2.043




Xzz -
 4.303
 -
 4.303




ETA -
 0.0509
 -
 0.0506




Øz,a
21.58
21.55




Øa,CN
22.16
22.11




Øz,CN
  0.58
  0.56



 








   








 








   








Table 2. Nitrogen nqcc's in synclinal 3-Fluoropropionitrile (MHz).  Calculation was made on approximate equilibrium re(1) and re(2) structures.
   











Calc / re(1)
Calc / re(2)
Expt.
   








14N Xaa -
 1.924
 -
 1.922




Xbb -
 0.056
 -
 0.059




Xcc
1.980
1.981




Xab -
 2.995
 -
 2.996




Xac
0.858
0.855




Xbc
0.516
0.516



 









RSD
0.030 (1.3 %)
0.030 (1.3 %)



 









Xxx
2.235
2.234




Xyy
2.051
2.052




Xzz -
 4.286
 -
 4.286




ETA -
 0.0429
 -
 0.0424




Øz,CN
  0.11
  0.12



 









 








 




Table 3.  3-Fluoropropionitrile.  Heavy atom structure parameters, approximate re(1) and re(2) (Å and degrees).  Complete structures are given here:  antiperiplanar, synclinal.
 




    antiperiplanar
 re(1)  re(2)






FC(1) 1.3797
1.3796

C(1)C(2) 1.5195
1.5192

C(2)C(3) 1.4590
1.4593

C(3)N 1.1557
1.1558

FC(1)C(2) 108.17
108.20

C(1)C(2)C(3) 110.22
110.24

C(2)C(3)N 177.83
177.88

FC(1)C(2)C(3) 180.
 180.

C(1)C(2)C(3)N     0.
     0.
 




      synclinal
 re(1)  re(2)






FC(1) 1.3782
 1.3778

C(1)C(2) 1.5164
 1.5161

C(2)C(3) 1.4604
 1.4604

C(3)N 1.1557
 1.1557

FC(1)C(2) 109.42
 109.41

C(1)C(2)C(3) 112.07
 112.02

C(2)C(3)N 179.26
 179.35

FC(1)C(2)C(3)   65.64
   65.40

C(1)C(2)C(3)N   49.76
   50.79








 








 













Table 4.  3-Fluoropropionitrile.  Rotational Constants (MHz).











antiperiplanar
 Calc re(1) Calc re(2) Expt [1]






A
 27219.4
 27261.3
 27009(11)

B
   2309.8
   2308.9
 2292.0710(76)

C
   2187.5
   2186.9
 2170.9069(76)

 



synclinal
 Calc re(1) Calc re(2) Expt [1]






A
 11631.1
 11618.0
 11635.6040(46)

B
   3215.9
   3222.5
 3178.2835(12)

C
   2733.6
   2736.8
 2705.7206(11)



 








 








[1] H.Møllendal, S.Samdal, and J.-C.Guillemin, J.Phys.Chem. A 116,1015(2012).

 








 








CH3CN
 CH3CH2CN
 CF3CN CF3CF2CN

 








 








Table of Contents




Molecules/Nitrogen




 








 













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Last Modified 27 Dec 2011