




















SPCl_{3} 



















Chlorine 



Nuclear
Quadrupole Coupling Constants 



in Thiophosphoryl Chloride 

































Calculation was made here of the chlorine nqcc's in thiophosphoryl
chloride on the equilibrium and average molecular structures derived by Firth
and Davis [1]. These are given in Table 1 and 2. Structure parameters
are compared in Table 3, atomic coordinates for the equilibrium structure
are given in Table 4. 






















Coordinate Systems 












X_{uu} is the component of the nqcc tensor along the threefold
symmetry axis. Corresponding to the atomic coordinates given below
in Table 4, X_{vv} and X_{ww} are the components along the
v and w axes for the Cl atom in the uvplane. 












The subscripts x,y,z refer to the principal axes of the nqcc
tensor. The nqcc yaxis is chosen coincident with the waxis.
Ø (degrees) is the angle between its subscripted parameters.
ETA = (X_{xx}  X_{yy})/X_{zz}. 































Table 1. Chlorine nqcc's in SPCl_{3} (MHz). Calculation was made on
the r_{e} structure [1]. 













Calc. 

Expt. 










^{35}Cl 
X_{uu} 

14.71 





X_{vv} 
 
43.31 





X_{ww} 

28.60 





X_{uv} 

35.69 













X_{xx} 

31.69 





X_{yy} 

28.60 





X_{zz} 
 
60.29 





ETA 
 
0.051 





Ø_{z,u} 

64.55 





Ø_{u,PCl} 

63.65 





Ø_{z,PCl} 

0.90 












^{37}Cl 
X_{uu} 

11.59 





X_{vv} 
 
34.14 





X_{ww} 

22.54 





X_{uv} 

28.12 


































The pyramid formed by the zprincipal axes of the three Cl
nqcc tensors is somewhat 'flatter' than the molecular pyramid.
This is typical of the pyramidal trichlorides. 































Table 2. Chlorine nqcc's in SPCl_{3} (MHz). Calculation was made on
the r_{z} structure [1]. 













Calc. 

Expt. 










^{35}Cl 
X_{uu} 

14.83 





X_{vv} 
 
43.63 





X_{ww} 

28.80 





X_{uv} 

35.89 












^{37}Cl 
X_{uu} 

11.69 





X_{vv} 
 
34.38 





X_{ww} 

22.70 





X_{uv} 

28.28 






































Table 3. Molecular structure parameters (Å and degrees). 






r_{e }[1] 
r_{z }[1] 





SP 
1.8805 
1.8835 

PCl 
2.0042 
2.0093 

SPCl 
116.35 
116.35 





















Table 3. Atomic coordinates, r_{e} 
(More figures are shown than are significant.) 











u (Å) 

v (Å) 

w (Å) 









Cl 
 
0.703204 

1.795994 

0.0 

Cl 
 
0.703204 
 
0.897997 
± 
1.555376 

P 

0.186304 

0.0 

0.0 

S 

2.066804 

0.0 

0.0 























[1] S.Firth and R.W.Davis, J.Mol.Spectrosc. 179,32(1996). 






















NCl_{3}_{} 
PCl_{3} 
_{}CHCl_{3} 
SiHCl_{3} 


AsCl_{3} 
OPCl_{3}_{} 
CFCl_{3} 
CH_{3}CCl_{3} 






















Table of Contents 





Molecules/Chlorine 






























SPCl3.html 






Last
Modified 3 June 2003 









