




















H_{2}Si=S 


































Deuterium 



Nuclear
Quadrupole Coupling Constants 



in
Silanethione 

































Calculation was made here of the D
and ^{33}S nqcc tensors on the semiexperimental equilibrium
structure
of Thorwirth et al. [1]. These are compared with the (limited)
experimental values [2] in Tables 1 and 2. 












In Table 1, 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 aaxis is coincident with the
twofold
symmetry axis. The nqcc yaxis is chosen coincident with the
inertia
caxis, which is perpendicular to the plane of the molecule.
Ø
(degrees) is the angle between its subscripted parameters. ETA =
(X_{xx}
 X_{yy})/X_{zz}. 


RSD is the calibration residual
standard deviation for the B3LYP/631G(df,3p) model for calculation of
the nqcc's, which may be taken as an estimate of the uncertainty in the
calculated nqcc's. 































Table 1. Deuterium nqcc's
in D_{2}Si=S_{ }(kHz). Calculation was made
on the r_{e}^{se} structure [1]. 













Calc. 

Expt. [2] 










^{2}H 
X_{aa} 

 2.0 





X_{bb} 

48.4 

70.2(30) 



X_{cc} 
 
46.4 





X_{ab} 
± 
67.4 













RSD 

1.1 (0.9 %) 













X_{xx} 
 
48.8 





X_{yy} 
 
46.4 





X_{zz} 

95.2 





ETA 
 
0.026 





Ø_{z,a} 

55.24 





Ø_{a,SiD} 

55.16 





Ø_{z,SiD} 

0.08 













































Table 2. ^{33}S
nqcc's in H_{2}Si=S_{ }(MHz). Calculation was
made on the r_{e}^{se} structure [1]. 














[a] B3LYP/6311G(3df,3p) model. 




[b] B3LYP/TZV+(3df,3p) model. 















Calc [a] 

Calc [b] 

Expt. [2] 












^{33}S 
X_{aa} 

 9.94


 9.96 
 
9.5077(40) 



X_{bb} 

26.44 

26.55 





X_{cc} 
 
16.50 
 
16.58 




































Structure parameters, r_{e}^{se}
[1] 
Si=S = 1.9357(1) Å 






SiH = 1.4735(1) Å 






HSH = 110.33(1)^{o} 






















[1] S.Thorwirth, J.Gauss,
M.C.McCarthy, F.Shindo, and P.Thaddeus, Chem.Comm. 5292(2008). 


[2] M.C.McCarthy, C.A.Gottlieb,
P.Thaddeus,
S.Thorwirth, and J.Gauss, J.Chem.Phys. 134,034306(2011). 






















H_{2}O 
H_{2}C=O 
H_{2}C=S 
H_{2}Si=O
^{} 






















Table of Contents 





Molecules/Deuterium 






























H2SiS.html 






Last
Modified 16 Feb 2009 









