S(CN)2
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Nitrogen


Nuclear Quadrupole Coupling Constants


in Sulfur Dicyanide


 








 








Calculation of the 14N nqcc's in sulfur dicyanide was made on the rs/re structure of Demaison et al. [1] and on each of several structure types derived by Kisiel et al. [2], including an ropt structure given by CCSD(T)/aug-cc-pVTZ optimization.  These calculated nqcc's are compared with the experimental values of Pierce et al. [3] in Tables 1 and 2.  Structure parameters are given in Table 3.


 









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.  The nqcc y-axis is chosen coincident with the inertia c-axis, these are perpendicular to the plane of the molecule.  (degrees) is the angle between its subscripted parameters. ETA = (Xxx - Xyy)/Xzz.

RMS is the root mean square difference between calculated and experimental diagonal nqcc's (percentage of average experimental nqcc).  RSD is the residual standard deviation of the calibration of the B3PW91/6-311+G(df,pd) model for calculation of the efg's/nqcc's.

 








 








   








Table 1.  Nitrogen nqcc's in S(C14N)2 (MHz).  Calculation was made on the ropt = CCSD(T)/aug-cc-pVTZ structure of Kisiel et al. [2], and on the re/rs structure of Demaison et al. [1].
   










Calc / ropt

Calc / re/rs
Expt. [3]
   








Xaa - 1.529 - 1.532 - 1.51

Xbb
0.357
0.351
0.30

Xcc
1.172
1.181
1.21

Xab 3.488 3.509












RMS
0.041 (4.1 %) 0.037 (3.6 %)


RSD
0.030 (1.3 %) 0.030 (1.3 %)


 







Xxx
3.027

3.043



Xyy
1.172
1.181



Xzz -
4.200
- 4.224



ETA -
0.442
- 0.441



z,a
37.43

37.49



a,CN
36.48

36.44



z,CN
  0.95

  1.04



 







   








 








   








Table 2.  Nitrogen nqcc's in S(C14N)2 (MHz).  Calculation was made on the ro, rs, rm(1), and reSE structures of Kisiel et al. [2].
   










Calc / ro
Calc / rs
Expt. [3]
   








Xaa - 1.600 - 1.612 - 1.51

Xbb
0.435
0.423
0.30

Xcc
1.165
1.189
1.21

Xab 3.502 3.510












RMS
0.097 (9.7 %) 0.092 (9.2 %)


RSD
0.030 (1.3 %) 0.030 (1.3 %)


 









Calc / rm(1)
Calc / reSE












Xaa -
1.614
-
1.599




Xbb
0.437

0.434




Xcc
1.177

1.165




Xab 3.508
3.500













RMS

0.101 (10. %)

0.096 (9.6 %)




RSD

0.030 (1.3 %)
0.030 (1.3 %)



 








 














Table 3.  Molecular structure parameters ( and degrees).  Note: CN tilts outward.







ropt [2]  re/rs [1] rs [2]






CS 1.7059 1.700  ( rs ) 1.701(5)

CN 1.1617 1.160 1.158(6)

CSC   97.77   97.55   98.2(3)

SCN 175.37 175.22 175.0(6)







ro [2]rm(1) [2]
reSE [2]






CS
1.698(6)
1.6985(13)
1.6972(4)

CN
1.160(9)
1.1587(10)
1.1602(4)

CSC
  98.6(5)
  98.48(8)
  98.36(3)

SCN
175.4(11)
175.19(12)
175.14(5)







 








 








[1] J.Demaison, G.Wlodarczak, H.Rck, K.H.Wiedenmann, and H.D.Rudolph, J.Mol.Struct. 376,399(1996).

[2] Z.Kisiel, M.Winnewisser, B.P.Winnewisser, F.C.De Lucia, D.Tokaryk, and B.E.Billinghurst, J.Phys.Chem. A 117,13815(2013)   and   Z.Kisiel, O.Dorosh, M.Winnewisser, M.Behnke, I.R.Medvedev, and F.C.De Lucia, J.Mol.Spectrosc. 246,39(2007).


[3] L.Pierce, R.Nelson, and C.Thomas, J.Chem.Phys. 43,3423(1965).

 









 








O=C(CN)2 H2C(CN)2 H2C=C(CN)2


 








 








Table of Contents




Molecules/Nitrogen




 








 













SCNCN.html






Last Modified 24 Oct 2017