CH2Cl-CH=CH2
































 









Chlorine


Nuclear Quadrupole Coupling Constants

in cis-3-Chloropropene

 








 

 





Chlorine nqcc's in c-3-chloropropene were determined by Hirota [1].

 








Calculation of the nqcc tensor was made here on molecular structures given by MP2/aug-cc-pVTZ(G03) and MP2/6-311+G(3df,3pd) optimizations; and on these same structures but with ~re bond lenghts for C-C, C=C, and CCl.  These calculated nqcc's are compared with the experimental values in Tables 1 - 4.  Structure parameters are given in Table 5, rotational constants in Table 6.

 








In Tables 1 - 4, subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  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 of the B1LYP/TZV(3df,2p) model for calculation of the nqcc's, which may be taken as an estimate of the uncertainty in the calculated nqcc's.

 








 








   







Table 1.  35Cl nqcc's in c-3-Chloropropene (MHz).  

 







Calc (1) was made on the MP2/aug-cc-pVTZ(G03) optimized molecular structure.

Calc (2) was made on this same structure but with ~re bond lenghts for C-C, C=C, and CCl.

 









Calc (1)
Calc (2)
Expt. [1]
   







Xaa - 18.62 - 18.59 - 18.19

Xbb - 18.26 - 18.23 - 17.89

Xcc
36.89
36.82
35.99

|Xab|
54.47
54.37



 







RMS
0.62 (2.6 %)
0.56 (2.3 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
36.02
35.96



Xyy
36.89
36.82



Xzz - 72.91 - 72.78



ETA
0.0119
0.0118



Øz,a
44.90
44.90



Øa,CCl
45.42
45.42



Øz,CCl
  0.51
  0.52



 
 






 








 








   







Table 2.  37Cl nqcc's in c-3-Chloropropene (MHz).  

 







Calc (1) was made on the MP2/aug-cc-pVTZ(G03) optimized molecular structure.

Calc (2) was made on this same structure but with ~re bond lengths for C-C, C=C, and CCl.

 









Calc (1)
Calc (2)
Expt.
   







Xaa - 15.27 - 15.24



Xbb - 13.80 - 13.77



Xcc
29.07
29.02



|Xab|
42.92
42.84



 







RSD
0.44 (1.1 %)
0.44 (1.1 %)



 
 






 








 








   







Table 3.  35Cl nqcc's in c-3-Chloropropene (MHz).  

 







Calc (1) was made on the MP2/6-311+G(3df,3pd) optimized molecular structure.

Calc (2) was made on this same structure but with ~re bond lengths for C-C, C=C, and CCl.

 









Calc (1)
Calc (2)
Expt. [1]
   







Xaa - 18.70 - 19.04 - 18.19

Xbb - 18.11 - 17.84 - 17.89

Xcc
36.81
36.88
35.99

|Xab|
54.28
54.39



 







RMS
0.57 (2.4 %)
0.71 (3.0 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
35.88
35.95



Xyy
36.81
36.87



Xzz - 72.69 - 72.83



ETA
0.0128
0.0127



Øz,a
44.84
44.68



Øa,CCl
45.41
45.25



Øz,CCl
  0.57
  0.57



 
 





   








 








   







Table 4.  37Cl nqcc's in c-3-Chloropropene (MHz).  

 







Calc (1) was made on the MP2/6-311+G(3df,3pd) optimized molecular structure.

Calc (2) was made on this same structure but with ~re bond lengths for C-C, C=C, and CCl.

 









Calc (1)
Calc (2)
Expt.
   







Xaa - 15.33 - 15.59



Xbb - 13.68 - 13.47



Xcc
29.01
29.06



|Xab|
42.77
42.85



 







RSD
0.44 (1.1 %)
0.44 (1.1 %)



 
 






 








 












Table 5.  cis-3-Chloropropene.  Heavy atom structure parameters (Å and degrees).  Complete structures are given here in Z.matrix format.
 



r (1) = MP2/aug-cc-pVTZ(G03) opt.

r (2) = r (1) but with ~re bond lengths for C-C, C=C, and CCl.
 


Point Group CS
  r (1)   r (2)





ClC(3) 1.7817 1.7784
C(3)C(2) 1.4941 1.4932
C(2)C(4) 1.3327 1.3289
ClC(3)C(2) 113.92 113.92
C(3)C(2)C(4) 126.65 126.65
 

r (1) = MP2/6-311+G(3df,3pd) opt.
r (2) = r (1) but with MP2/6-311+G(3df,3pd) ~re bond lengths for C-C, C=C, and CCl.




  r (1)   r (2)



ClC(3) 1.7728 1.7773
C(3)C(2) 1.4943 1.4935
Click on image to enlarge. C(2)C(4) 1.3316 1.3287

ClC(3)C(2) 114.27 114.27

C(3)C(2)C(4) 126.72 126.72


 








 













Table 6.  cis-3-Chloropropene.  Rotational constants (MHz).  35Cl species.
 




r (1) = MP2/aug-cc-pVTZ(G03) opt.

r (2) = r (1) but with ~re C-C, C=C, and CCl bond lengths.







  r (1)   r (2)     Expt. [1]






A 13 589.1 13 640.2 13 580.58(44)

B   3 860.8   3 870.5   3 816.71(38)

C   3 063.7   3 072.4   3 035.15(38)
 
 


r (1) = MP2/6-311+G(3df,3pd) opt.

r (2) = r (1) but with ~re C-C, C=C, and CCl bond length.







  r (1)   r (2)    Expt. [1]






A 13 694.8 13 699.0 13 580.58(44)

B   3 854.7   3 849.8   3 816.71(38)

C   3 065.1   3 062.2   3 035.15(38)


 








 








[1] E.Hirota, J.Mol.Spectrosc. 35,9(1970).

 








E.B.Kent, M.N.McCabe, M.A.Phillips, B.P.Gorden, and S.T.Shipman, 66th OSU International Symposium on Molecular Spectroscopy, 2011, Abstract RH01.

 








 








gauche-3-Chloropropene gauche-3-Bromopropene



 








 








Table of Contents




Molecules/Chlorine




 








 













3ClPropene.html






Last Modified 9 April 2008