O=CCl2





 









Chlorine


Nuclear Quadrupole Coupling Constants


in Phosgene


 








 








 








In the following Tables, 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. 

 








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.  (degrees) is the angle between its subscripted parameters.  ETA = (Xxx - Xyy)/Xzz.

 








 








   







Table 1. Chlorine nqcc's in OC35Cl2 (MHz).  Calculation was made on the equilibrium structure of Nakata et al. [2].
   










Calc.
Expt. [1]
   







35Cl Xaa - 37.28 - 37.641(25)


Xbb
11.16
10.337(29)


Xcc
26.12
27.304(16)


Xab 53.62
51.0(16)

 







RMS
0.86 (3.4 %)




RSD
0.49 (1.1 %)



 







Xxx
45.78
42.7(14)


Xyy
26.12
27.304(16)


Xzz - 71.90 - 70.1(14)


ETA - 0.273 - 0.220(21)


z,b
57.16
57.6(3)


b,CCl
55.90




z,CCl
  1.26



 







 








 








The angle between the two z-axes is 2.52o larger than the ClCCl angle.  This is typical of  the XCl2 dichloride moiety.

 








 








 
   







Table 2. Chlorine nqcc's in OC35Cl37Cl (MHz).  Calculation was made on the equilibrium structure of Nakata et al. [2].
   










Calc.
Expt. [1]
   







35Cl Xaa - 35.60 - 36.009(36)


Xbb
  9.48
  8.705(39)


Xcc
26.12
27.304(16)


|Xab|
54.35
51.8(16)

 







RMS
0.85 (3.5 %)




RSD
0.49 (1.1 %)



 






37Cl Xaa - 30.70 - 30.899(67)


Xbb
10.11
  9.379(69)


Xcc
20.59
21.520(13)


|Xab|
41.64
39.6(12)

   






RMS
0.69 (3.4 %)




RSD
0.44 (1.1 %)



 







 








 












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




 re [2]  re [3]





O=C 1.1756 1.1766(22)

CCl 1.7381 1.7365(12)

ClCCl 111.79

OCCl
124.05(6)


 








 








[1] A.C.Ferguson and W.H.Flygare, J.Phys.Chem. 83,3161(1979).

[2] M.Nakata, T.Fukuyama, K.Kuchitsu, H.Takeo, and C.Matsumura, J.Mol.Spectrosc. 83,118(1980).

[3] S.Yamamoto, M.Nakata, and K.Kuchitsu, J.Mol.Spectrosc. 112,173(1985).

 








J.H.Carpenter and D.F.Rimmer, J.Chem.Soc. Farad.Trans. 2 74,466(1978): ro structure.


 









 









SCCl2 SCFCl OCBr2 CH3COCl

HCOCl FCOCl s-t-CH2CHCOCl

 








 








Table of Contents




Molecules/Chlorine




 








 













OCCl2.html






Last Modified 4 June 2003