SO2ClF































 









Chlorine


Nuclear Quadrupole Coupling Constants


in Sulfuryl Chloride Fluoride


 








 








 








Chlorine nqcc's in SO2ClF, as well as an equilibrium structure, were determined by Müller and Gerry [1].  Calculation of the nqcc's was made here on this re structure, and on an ropt structure given by MP2/6-311+G(3df) optimization.  These are compared with the experimental values in Tables 1 and 2.  Structure parameters are given in Table 3.  The results of B3LYP/cc-pVTZ calculation of centrifugal distortion constants are compared with experimental results in Table 4.

 








In Tables 1 and 2, subscripts a,b,c refer to the principal axes of the inertia tensor; 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 molecular symmetry plane.  Ø (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 the average of the magnitudes of the experimental nqcc's).  RSD is the calibration residual standard deviation for the B1LYP/TZV(3df,2p) model for calculation of the chlorine efg's/nqcc's. 

 








 







 
   








Table 1. Chlorine nqcc's in SO2ClF (MHz).  Calculation was made on re and ropt structures.
   











Calc /re
Calc /ropt
Expt. [1]
   








35Cl Xaa - 76.70 -
 77.25
 - 76.55160(29)


Xbb
35.59
35.89
35.72334(45)


Xcc
41.11
41.36
40.82826(45)


Xab
- 6.45
- 6.60



 









RMS
0.20 (0.39 %)
0.52 (1.0 %)




RSD
0.49 (1.1 %)
0.49 (1.1 %)



 









Xxx
35.96
36.28




Xyy
41.11
41.36




Xzz - 77.07 -
 77.63




ETA
0.0667
0.0654




Øz,a
3.277
3.328




Øa,SCl
3.977






Øz,SCl
0.700





   







37Cl Xaa - 60.45 -
 60.88
 - 60.32918(28)


Xbb
28.05
28.28
28.15011(46)


Xcc
32.40
32.60
32.17907(46)


Xab
- 5.12
- 5.25



 









RMS
0.16 (0.39 %)
0.41 (1.0 %)




RSD
0.44 (1.1 %)
0.44 (1.1 %)



 









 








 








   








Table 2. Chlorine nqcc's in SO18OClF (MHz). Calculation was made on re and ropt structures.
   











Calc /re
Calc /ropt
Expt. [1]
   








35Cl Xaa - 76.78 -
 77.33
 - 76.60849(51)


Xbb
39.61
39.92
39.39199(80)


Xcc
37.17
37.40
37.21650(80)


Xab
- 0.29
- 0.35




Xac
- 5.81
- 5.95




Xbc
  2.33
  2.27
  2.223(32) *

 









RMS
0.16 (0.31 %)
0.53 (1.0 %)




RSD
0.49 (1.1 %)
0.49 (1.1 %)



   







37Cl Xaa - 60.51 -
 60.94
 - 60.37657(54)


Xbb
31.21
31.46
31.04700(87)


Xcc
29.29
29.48
29.32957(87)


Xab
- 0.11
- 0.15




Xac
- 4.60
- 4.71




Xbc
  1.84
1.80
  1.768(40) *

 









RMS
0.12 (0.31 %)
0.41 (1.0 %)




RSD
0.44 (1.1 %)
0.44 (1.1 %)



 









 








* Absolute value.

 








 


Table 3.  SO2ClF Molecular structure parameters re [1], and  ropt = 6-311+G(3df) optimization (Å and degrees).
 




    re  ropt

SO 1.405431.4130

SCl 1.985711.9900

SF 1.548951.5590

OSO 124.039124.36

ClSO 108.979108.82

FSO 106.961107.00

ClSF   97.673  97.36


 








 








 




Table 4.  SO2ClF  Centrifugal Distortion Constants (kHz).  Calc = B3LYP/cc-pVTZ
 







Calc
  Expt [1]







D_J
0.504
0.47931(103)

D_JK
1.99
2.0282(57)

D_K - 1.58 - 1.5653(147)

d_1
0.00360
0.00336(84)

d_2
0.00553
0.00593(76)


 








 








[1]  H.S.P.Müller and M.C.L.Gerry, J.Chem.Soc. Faraday Trans. 90,2601(1994).

 








C.W.Holt amd M.C.L.Gerry, Chem.Phys.Lett. 9.621(1971).

 








SCl2 ClSCN CH3SCl NSCl

ClSF O=SCl2 ClSSCl SO2Cl2

 








 








Table of Contents




Molecules/Chlorine




 








 













SO2ClF.html






Last Modified 24 March 2015