SCl2


























 









Chlorine


Nuclear Quadrupole Coupling Constants


in Sulfur Dichloride


 








 








 








Calculation was made of the Cl nqcc tensors in sulfur dichloride on the substitution structure of Bizzocchi et al. [1], and on the CCSD(T)(ae)/cc-pCVQZ equilibrium structure of Coriani et al. [2].  These are compared with the experimental nqcc's of Merke and Dreizler [3] in Tables 1 - 3.  Structure parameters are given in Table 4.

 








In Tables 1 - 3, 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 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 nqcc's, which may be taken as an estimate of the uncertainty in the calculated nqcc's.

 








 








 
   








Table 1. 35Cl nqcc's in S35Cl2 (MHz).  Calculation was made on the rs molecular structure of Bizzocchi et al. [1], and the ab initio re structure of Coriani et al. [2].
   










Calc. rs
Calc. re
Expt. [3]
   








Xaa - 38.86 - 38.90 - 38.671(11)

Xbb
- 9.32
- 9.31
- 9.1231(43)

Xcc
48.19
48.22
47.7945(66)

Xab ± 53.86 ± 53.92 ± 53.76(23)

 







RMS
0.28 (0.87 %)
0.30 (0.94 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
31.76
31.80
31.86(23)

Xyy
48.19
48.22
47.7945(66)

Xzz - 79.94 - 80.02 - 79.65(23)

ETA
0.205
0.205



Øz,a
37.33
37.33
37.317(31)

Øa,SCl
38.64
38.65



Øz,SCl
  1.31
  1.32
  1.3

 








 








The angle between the two z-axes is 2.6o larger than the ClSCl angle.  This is typical of  the XCl2 dichloride moiety.

 








 








   








Table 2.  Chlorine nqcc's in S35Cl37Cl (MHz).  Calculation was made on the rs molecular structure of Bizzocchi et al. [1], and the ab initio re structure of Coriani et al. [2].
   










Calc. rs
Calc. re
Expt.
   








Xaa(35Cl) - 37.95 - 37.98



Xbb - 10.24 - 10.24



Xcc
48.19
48.22



Xab +/-
54.10 +/- 54.16



 







RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xaa(37Cl) - 31.35
31.38



Xbb
- 6.62
- 6.62



Xcc
37.98 - 38.00



Xab -/+ 42.24 -/+ 42.29



 







RSD
0.44 (1.1 %)
0.44 (1.1 %)



 








 








 








   








Table 3. 37Cl nqcc's in S37Cl2 (MHz).  Calculation was made on the rs molecular structure of Bizzocchi et al. [1], and the ab initio re structure of Coriani et al. [2].
   










Calc. rs
Calc. re
Expt.
   








Xaa - 30.63 - 30.66



Xbb
- 7.35
- 7.34



Xcc
37.98
38.00



Xab ± 42.45 ± 42.49



 







RSD
0.44 (1.1 %)
0.44 (1.1 %)



 


















 


Table 4.  Sulfur dichloride.  Molecular structure parameters (Å and degrees).
 




  rs [1]   re [2]





SCl 2.0128(11) 2.014176

ClSCl 102.71(9)
102.706


 








 








[1] L.Bizzocchi, L.Cludi, C.Delgi Esposti, and A.Giorgi, J. Mol. Spectrosc. 204,275(2000).

[2] S.Coriani, D.Marchesan, J.Gauss, C.Hättig, T.Helgaker, and P.Jørgensen, J.Chem.Phys. 123,184107(2005).

[3] I.Merke and H.Dreizler, Z.Naturforsch. 47a,1141(1992).

 








R.W.Davis and M.C.L.Gerry, J.Mol.Spectrosc. 65,455(1977).  Partial rs and average structures.

J.T.Murray, W.A.Little Jr., Q.Williams, and T.L.Weatherly, J.Chem.Phys. 65(3),985(1976): In S35Cl2, Xaa = -38.98(10), Xbb = -8.87(10), Xcc = 47.95(10), and |Xab| = 64(10) MHz.


 









 








OCl2 OCCl2 SCCl2 HOCl

 








 








Table of Contents




Molecules/Chlorine




 








 













SCl2.html






Last Modified 27 Jan 08