CH2=C(H)CH2CH2CN































 









Nitrogen


Nuclear Quadrupole Coupling Constants


in 4-Pentenenitrile


 








 








 








Nitrogen nqcc'c in the eg- conformer of 4-pentenenitrile - as well as in each of the four conformers listed below - were determined by Hays et al. [1].













eg+
 et
 st
 sg-













Calculation was made here of the nitrogen nqcc tensors in the eg- conformer of 4-pentenenitrile on an approximate equilibrium (~re)  molecular structure given by MP2/6-311+G(3df,3pd) optimization with empirically corrected bond lengths. These calculated nqcc's are compared with the experimental values in Table 1.  Structure parameters are given in Table 2, rotational constants in Table 3.











In Table 1, subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  ETA = (Xxx - Xyy)/Xzz.  Ø (degrees) is the angle between its subscripted parameters.  RMS is the root mean square difference between calculated and experimental diagonal nqcc's (percentage of the average of the magnitudes of the experimental nqcc's).  RSD is the calibration residual standard deviation of the B3PW91/6-311+G(df,pd) model for calculation of nitrogen efg's/nqcc's.

 








 







 
   






Table 1.  Nitrogen nqcc's in eg- 4-Pentenenitrile (MHz).  Calculation was made on ~re molecular strcuture.
   









Calc
Expt. [1]
   






14N Xaa
0.614
0.553(11)


Xbb - Xcc -
 4.687
 -
 4.639(19)


Xbb -
 2.650
 -
 2.596 *


Xcc
2.036
2.043 *


Xab
2.687




Xac -
 0.347




Xbc
0.482












RMS
0.047 (2.7 %)




RSD
0.030 (1.3 %)












Xxx
2.177




Xyy
2.041




Xzz -
 4.218




ETA
 -
 0.0320




Øz,CN
0.50












 








* Derived here from Xaa and Xbb - Xcc















Table 2.  4-Pentenenitrile, eg-:   MP2/6-311+G(3df,3pd) opt structure parameters, approximate equilibrium bond lengths are given in parentheses (Å and degrees).






 C
 C,1,B1
 C,2,B2,1,A1
 C,3,B3,2,A2,1,D1,0
 C,4,B4,3,A3,2,D2,0
 N,5,B5,4,A4,3,D3,0
 H,1,B6,2,A5,3,D4,0
 H,1,B7,2,A6,3,D5,0
 H,2,B8,1,A7,3,D6,0
 H,3,B9,2,A8,1,D7,0
 H,3,B10,2,A9,1,D8,0
 H,4,B11,3,A10,2,D9,0
 H,4,B12,3,A11,2,D10,0






 B1=1.33404301         (1.3310)
 B2=1.49459382         (1.4938)
 B3=1.53869668         (1.5358)
 B4=1.45971945         (1.4606)
 B5=1.16970672         (1.1563)
 B6=1.08205186
 B7=1.08035571
 B8=1.08584353
 B9=1.09120021
 B10=1.09016786
 B11=1.08993613
 B12=1.09052547
 A1=123.92131275
 A2=111.5097904
 A3=111.10398112
 A4=178.33233464
 A5=120.98191639
 A6=121.34848013
 A7=119.33718633
 A8=110.46836124
 A9=110.10781095
 A10=110.5596285
 A11=110.2668621
 D1=109.39965916
 D2=-64.12534762
 D3=-25.5763411
 D4=1.58761071
 D5=-178.12764186
 D6=177.60737859
 D7=-130.95157691
 D8=-11.97244632
 D9=175.23673862
 D10=56.36978573







 













Table 3.  4-Pentenenitrile, eg-:  Rotational Constants (MHz).  Calc is ~re structure.

 





Calc
    Expt [1]







A 5663.
 5804.3411(58)


B 2637.
 2491.5640(19)


C 1959.
 1892.2972(17)







 








 








[1] P.Mishra, S.M.Fritz, B.M.Hays, D.Mehta-Hurt, K.M.Jawad, and T.S.Zwier, PCCP xxx,xxx(2019).

 








B.M.Hays, D.Mehta-Hurt, K.M.Jawad, A.O.Hernandez-Castillo, C.Abeysekera, D.Zhang, and  T.S.Zwier, Abstract WC01, 72nd ISMS, Champaign-Urbana, Illinois, 2017.

 








 








Table of Contents




Molecules/Nitrogen




 








 













4PN_egminus.html






Last Modified 16 Oct 2019