CH2CH2CHCl




 









Chlorine


Nuclear Quadrupole Coupling Constants


in Cyclopropyl Chloride


 







 
 
Calculation of the chlorine nqcc's in cyclopropyl chloride was made on the substitution structure of Schwendeman et al. [1], and on an ropt structure obtained by MP2/6-311+G(2d,p) optimization.  These are compared with the experimental nqcc's in Tables 1 and 2.  Structure parameters are compared in Table 3.
 
In Tables 1 and 2, 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 inertia b-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 nqcc's. 

 







 
 
   







Table 1. Chlorine nqcc's in cyclic CH2CH2CHCl (MHz).  Calculation was made on the substitution molecular structure of Schwendeman et al. [1].
   










Calc.
Expt. [1]
   






35Cl Xaa - 56.78 - 56.64(40)
Xbb 37.84 36.72(22)
Xcc 18.94 19.92(22)
|Xac| 39.23
 
RMS 0.86 (2.3 %)
RSD 0.49 (1.1 %)
 
Xxx 35.60 36.45 *
Xyy 37.84 36.72
Xzz - 73.44 - 73.17
ETA 0.030 0.004
Øz,a 23.01 22.85
Øa,CCl 21.8 21.8
Øz,CCl   1.2   1.0
   
37Cl Xaa - 44.86
Xbb 29.82
Xcc 15.04
|Xac| 30.81
 

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







Table 2. Chlorine nqcc's in cyclic CH2CH2CHCl (MHz).  Calculation was made on the MP2/6-311+G(2d,p) ropt molecular structure (see below).
   










Calc.
Expt. [1]
   






35Cl Xaa - 57.82 - 56.64(40)
Xbb 37.28 36.72(22)
Xcc 20.54 19.92(22)
|Xac| 37.40
 
RMS 0.84 (2.2 %)
RSD 0.49 (1.1 %)
 
Xxx 35.53 35.16 *
Xyy 37.28 36.72
Xzz - 72.81 - 71.88
ETA 0.024 0.022
Øz,a 21.84 22.17
Øa,CCl 21.28 21.28
Øz,CCl   0.55   0.89
 
 
* Calculated here from the experimental diagonal nqcc's and the calculated off-diagonal nqcc.
 
 
Table 3.  Molecular structure parameters (Å and degrees).      Z-Matrix
ropt = MP2/6-311+G(2d,p) optimization with corrected CCl bond length [2].
 
  rs [1]    ropt
C(1)Cl 1.740(3) 1.7508
C(1)C(2,3) 1.513(4) 1.4956
C(2)C(3) 1.515(1) 1.5178
CHs 1.079(1) 1.0808
CHc 1.086(4) 1.0818
CHt 1.082(3) 1.0825
CCCl 118.7(3) 119.06
ClCH 115.8(2) 111.60
CCHs 116.1(3) 118.88
C(1)C(3)Hc 115.5(2) 116.92
C(2)C(3)Hc 116.9(4) 116.87
C(1)C(3)Ht 117.8(4) 117.46
C(2)C(3)Ht 118.7(3) 118.75
HCH 116.2(3) 115.72
 
 

[1] R.H.Schwendeman, G.D.Jacobs, and T.M.Krigas, J.Chem.Phys. 40,1022(1964).
[2] I.Merke, L.Poteau, G.Wlodarczak, A.Bouddou, and J.Demaison, J.Mol.Spectrosc. 177,232(1996).

 








 








CH2CH2CCl2
 

 








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Molecules/Chlorine



 

 













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Last Modified 1 June 2006