cis-ClHC=CHF

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Chlorine


Nuclear Quadrupole Coupling Constants

in cis-1-Chloro-2-Fluoroethylene

 







 
 
The complete chlorine nqcc tensor in cis-1-chloro-2-fluoroethylene was determined by Dore et al. [1].  Several molecular structure types were derived by Puzzarini et al. [2].
 
Calculation of the nqcc's was made here on each of these several structures.  Chlorine nqcc's calculated on the equilibrium structure are compared with the experimental values in Table 1.  Results for the other structures are summarized in Table 2.  Equilibrium structure parameters are shown in Table 3.
 
In Table 1, 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 symmetry plane.  Ø (degrees) is the angle between its subscripted parameters.  ETA = (Xxx - Xyy)/Xzz.

 







 
 
   






Table 1. Chlorine nqcc's in c-ClHC=CHF (MHz).  Calculation was made on the equilibrium molecular structure of Puzzarini et al. [2].
   









Calc.
Expt. [1]
   





35Cl Xaa - 23.07 - 22.719(14)
Xbb - 9.75 10.600(13)
Xcc 32.83 33.319(17)
|Xab| 57.60 57.4770(86)
 
RMS 0.60 (2.7 %)
RSD 0.49 (1.1 %)
 
Xxx 41.57 41.136(13)
Xyy 32.83 33.319(17)
Xzz - 74.40 - 74.455(13)
ETA - 0.1175 - 0.10499(29)
Øz,a 41.70 41.9909(47)
Øa,PCl 42.4 42.4 *
Øz,PCl   0.7   0.4 *
   
37Cl Xaa - 18.71 - 18.488(63)
Xbb - 7.16 - 7.739(36)
Xcc 25.87 26.227(36)
|Xab| 45.33 45.403(86)
 
RMS 0.41 (2.4 %)
RSD 0.44 (1.1 %)
 
Xxx 32.76 32.606(92)
Xyy 25.87 26.227(36)
Xzz - 58.63 - 58.833(94)
ETA - 0.1175 - 0.1084(17)
Øz,a 41.37 41.625(23)
Øa,PCl 42.0 42.0 *
Øz,PCl   0.7   0.4 *
 

 
* Calculated here on re structure.
 
 
 
Table 2. The following molecular structure types of c-ClHC=CHF were derived by Puzzarini et al. [2].  For each, the RMS difference between calculated and experimental diagonal 35Cl nqcc's is given.
 
Structure Type RMS Difference
 
CCSD(T)/cc-pV(oo)Z 0.59 MHz (2.7 %)
Recommended re (Table 1) 0.60 MHz (2.7 %)
Kraitchman's rs 1.78 MHz (8.0 %)
Typke's rss 1.79 MHz (8.1 %)
Watson's rm(2) 0.82 MHz (3.7 %)
 
 
 
Table 3.  Molecular structure parameters re [2] (Å and degrees).
 
C(1)Cl 1.715(2)
C(1)H 1.077(1)
C=C 1.325(1)

C(2)F 1.331(1)
C(2)H 1.079(1)
ClC(1)C(2) 123.3(1)
HC(1)C(2) 120.4(1)
FC(2)C(1) 123.1(1)
HC(2)C(1) 122.9(1)
 
 

[1] L.Dore, C.Puzzarini, G.Cazzoli, and A.Gambi, J.Mol.Spectrosc. 204,262(2000).
[2] C.Puzzarini, G.Cazzoli, L.Dore, and A.Gambi, Phys.Chem.Chem.Phys. 3,4189(2001).

 








 








H2C=CHCl H2C=CCl2 cis-ClHC=CHCl
 

 








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Last Modified 15 July 2004