CH3SC(=O)Cl


















 





 





 









Chlorine


Nuclear Quadrupole Coupling Constants


in S-Methylchlorothioformate


 








 








 








Calculation of the chlorine nqcc tensors in CH3SC(=O)Cl was made here on a structure given by MP2/aug-cc-pVTZ optimization with approximate equilibrium CCl and C=O bond lengths.  These nqcc's are compared with experimental nqcc's [1] 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, subscripts x,y,z to the principal axes of the nqcc tensor.  The nqcc y-axis is chosen coincident with the c-axis.  Ø (degrees) is the angle between its subscripted parameters.  ETA = (Xxx - Xyy)/Xzz.

RMS is the root mean square difference between calculated and experimental nqcc's.  RSD is the residual standard deviation of the calibration of the B1LYP/TZV(3df,2p) model for calculation of the nqcc's, which may be taken as an estimate of the uncertainty in the calculated nqcc's.

 








 








   






Table 1.  Chlorine nqcc's in CH3SC(=O)Cl (MHz).
   









Calc
Expt [1]
   






35Cl Xaa -
 49.60
 -
 49.2(4)


Xbb
22.98
22.4(8)


Xcc
26.62
26.8


|Xab|
37.51



 







RMS
0.42 (1.3 %)




RSD
0.49 (1.1 %)



 







Xxx
38.88




Xyy
26.62




Xzz - 65.50




ETA -
 0.187




Øz,a
22.97




Øa,CCl
23.97




Øz,CCl
  1.00



 






37Cl Xaa -
 39.42
 -
 39.0(6)


Xbb
18.43
18.3(11)


Xcc
20.98
20.7


|Xab|
29.24




 






RMS
0.30 (1.2 %)




RSD
0.44 (1.1 %)




 






 








 


















Table 2.  CH3SC(=O)Cl  MP2/aug-cc-pVTZ optimized structure parameters (Å and degrees).  Approximate equilibrium CCl and C=O bond lengths are given in parentheses.
 












 Cl
 C,1,B1
 O,2,B2,1,A1
 S,2,B3,1,A2,3,D1,0
 C,4,B4,2,A3,1,D2,0
 H,5,B5,4,A4,2,D3,0
 H,5,B6,4,A5,2,D4,0
 H,5,B7,4,A6,2,D5,0
      Variables:
 B1=1.77730152      (1.7740)
 B2=1.19702498      (1.1892)
 B3=1.74519364
 B4=1.80694794
 B5=1.08739823
 B6=1.08577692
 B7=1.08577692
 A1=122.42587932
 A2=109.86412256
 A3=97.70160891
 A4=106.0650218
 A5=109.92074523
 A6=109.92074523
 D1=180.
 D2=180.
 D3=180.
 D4=-60.81310644
 D5=60.81310644
 










 








 








 


Table 3.  CH3SC(=O)35Cl  Rotational constants (MHz).






Calc
 Expt [1]





A
 6987.9
 6988.2(2)

B
 2045.8
 2033.458(5)

C
 1598.5
 1596.331(4)



 








 








[1] W.Caminati, R.K.Bohn, and N.True, J.Mol.Spectrosc. 84,355(1980).

 








 








CH3OC(=O)Cl HC(=O)Cl FC(=O)Cl CH3C(=O)Cl

 








 








Table of Contents




Molecules/Chlorine




 








 













CH3SCOCl.html






Last Modified 24 April 2013