CH2CHCl



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Chlorine


Nuclear Quadrupole Coupling Constants


in Vinyl Chloride


 











 





 








Vinyl chloride has been the subject of several microwave investigations [1-6]. Most recently, Hayashi and Inagusa [4] re-measured the chlorine nqcc's and determined a substitution molecular structure.  Merke et al. [5] and Demaison et al. [6] determined several molecular structures.

 
Chlorine nqcc's calculated on the substitution structure [4] are compared in Tables 1 and 2 with the experimental values [4].  Results of calculations on the structures of Merke et al. are shown in Table 3, and those on the structures of Demaison et al. in Table 4.  Substitution [4] and equilibrium [6] structure parameters are compared in Table 5.
   
In Tables 1 and 2, 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 computational model residual standard deviation. 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.  Ø (degrees) is the angle between its subscripted parameters.
    









   







Table 1.  35Cl nqcc's in CH2CHCl (MHz).  Calculation was made on the substitution structure of Hayashi and Inagusa [4].
   






 


Calc.
Expt. [4]

   







35Cl Xaa - 57.03 - 57.21(13)
 
Xbb
26.07

25.47

Xcc 30.96 31.74
|Xab| 36.10
  
RMS 0.58 (1.5 %)
RSD 0.49 (1.1 %)
  
Xxx 39.56 39.01 *
Xyy 30.96 31.74
 
Xzz -
70.52
-
70.75

ETA - 0.122 - 0.103
Øz,a 20.49 20.56
Øa,CCl 20.1 20.1
Øz,CCl   0.4   0.5
   

 








  * Calculated here from the experimental diagonal nqcc's and the calculated off-diagonal nqcc.
 
 
   







Table 2.  37Cl nqcc's in CH2CHCl (MHz).  Calculation was made on the substitution structure of Hayashi and Inagusa [4].
   






 


Calc.
Expt. [4]

   







37Cl Xaa - 45.06 - 45.13(11)
 
Xbb
20.66

20.25

Xcc 24.40 24.88
|Xab| 28.32
 
RMS 0.37 (1.2 %)
  RSD 0.44 (1.1 %)
 
Xxx 31.18 30.81 *
Xyy 24.40 24.88
 
Xzz -
55.58
-
55.69

ETA - 0.122 - 0.106
Øz,a 20.38 20.45
Øa,CCl 20.0 20.0
Øz,CCl   0.4   0.5
   
 
  * Calculated here from the experimental diagonal nqcc's and the calculated off-diagonal nqcc.
 
 
 
 
Table 3.  35Cl nqcc's in CH2CHCl (MHz).  The structures on which calculation was made are those according to Merke et al. [5].  RMS is the root mean square difference between calculated and experimental nqcc's [4].
 
Structure   Xaa   Xbb   Xcc RMS
 
ro -57.32 26.22 31.11 0.58
repislonI -57.27 26.26 31.02 0.62
rmrho (a/b) -57.15 26.32 30.84 0.72
rmrho (b/c) -56.97 26.09 30.88 0.62
rmrho (a/b/c) -57.03 26.14 30.88 0.64
near re -57.28 26.52 30.76 0.83
expt. nqcc's -57.21(13) 25.47 31.74
 
 
 
 
 
Table 4.  35Cl nqcc's in CH2CHCl (MHz).  The structures on which calculation was made are those according to Demaison et al. [6].  RMS is the root mean square difference between calculated and experimental nqcc's [4].
 
Structure   Xaa   Xbb   Xcc RMS
 
ro -57.35 26.20 31.15 0.55
rm(1) -57.10 26.18 30.92 0.63
rm(2) mod -57.20 26.26 30.93 0.66
rm(1L) -57.07 26.19 30.89 0.65
rs-fit  -57.18 26.15 31.02 0.57
re -57.09 26.30 30.79 0.73
expt. nqcc's -57.21(13) 25.47 31.74
  
 

 
Table 5.  Molecular structure parameters (Å and degrees).
 
rs [4] re [6]
C(1)Cl 1.726 1.7263
C=C 1.333 1.3262
CCCl 122.7 122.77
C(1)H 1.080 1.0784
CCH 123.1 123.86
CHt 1.079 1.0797
CHc 1.086 1.0795
CCHt 119.6 119.29
CCHc 121.1 121.80



 








 








[1] J.H.Goldstein and J.K.Bragg, Phys.Rev. 75, 1453(1949).

[2] D.Kivelson, E.B.Wilson Jr., and D.R.Lide Jr., J.Chem.Phys. 32,205 (1960).

[3] M.C.L.Gerry, Canad.J.Chem. 49,255(1971).

[4] M.Hayashi and T.Inagusa, J.Mol.Struct. 220,103(1990).
[5] I.Merke, L.Poteau, G.Wlodarczak, A.Bouddou, and J.Demaison, J.Mol.Spectrosc. 177,232(1996).
[6] J.Demaison, H.Møllendal, A.Perrin, J.Orphal, F.Kwabia Tchana, H.D.Rudolph, and F.Willaert, J.Mol.Spectrosc. 232,174(2005).

 








 








CH2CHBr CH2CCl2 c-ClHCCHCl CH3CH2Cl
CH2CHCN CH3Cl CH2CClCN

 








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Molecules/Chlorine




 








 













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Last Modified 4 July 2005