CH2Cl-CH=CH2
































 









Chlorine


Nuclear Quadrupole Coupling Constants

in gauche-3-Chloropropene



(Allyl Chloride, skew)



 








 

 





35Cl nqcc's in g-3-chloropropene were first determined by Hirota [1]. 35Cl and 37Cl nqcc's were subsequently determined by Kent et al. [2].

 








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 C-C, C=C, and CCl bond lengths.  These calculated nqcc's are compared with the experimental values [2] 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.  Øz,CCl (degrees) is the angle between the z-principal axis and the CCl bond direction.  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 g-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 C-C, C=C, and CCl bond lengths.

 









Calc (1)
Calc (2)
Expt. [2]
   







Xaa - 39.23 - 39.13 - 39.5(5)

Xbb
  3.00
  2.95
  3.5(4)

Xcc
36.23
36.18
36.1(6)

|Xab|
50.44  *
50.38  *



|Xac|
  2.67
  2.75



|Xbc|
  0.55
  0.60



 







RMS
0.34 (1.3 %)
0.38 (1.5 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
37.46
37.40



Xyy
35.40
35.35



Xzz - 72.86 - 72.75



ETA - 0.0283 - 0.0283



Øz,CCl
0.34
0.35



 
 






 








* The algabraic sign of the product XabXacXbc is negative.

 








 








   







Table 2.  37Cl nqcc's in g-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 C-C, C=C, and CCl bond lengths.

 









Calc (1)
Calc (2)
Expt. [2]
   







Xaa - 31.21 - 31.13 - 31.6(8)

Xbb
  2.65
  2.61
  3.1(10)

Xcc
28.56
28.52
28.5(13)

|Xab|
39.64  *
39.59  *



|Xac|
  1.91
  1.98



|Xbc|
  0.30
  0.34



 







RMS
0.34 (1.6 %)
0.39 (1.9 %)



RSD
0.44 (1.1 %)
0.44 (1.1 %)



 
 






 








* The algabraic sign of the product XabXacXbc is negative.

 








 








   







Table 3.  35Cl nqcc's in g-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 C-C, C=C, and CCl bond lengths.

 









Calc (1)
Calc (2)
Expt. [2]
   







Xaa - 38.76 - 38.94 - 39.5(5)

Xbb
  2.61
  2.72
  3.5(4)

Xcc
36.15
36.22
36.1(6)

|Xab|
50.54  *
50.58  *



|Xac|
  1.81
  1.80



|Xbc|
  0.02
  0.01



 







RMS
0.67 (2.5 %)
0.56 (2.1 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
37.39
37.44



Xyy
35.31
35.38



Xzz - 72.70 - 72.83



ETA - 0.0286 - 0.0282



Øz,CCl
0.36
0.36



 
 





   








* The algabraic sign of the product XabXacXbc is positive.

 








 








   







Table 4.  37Cl nqcc's in g-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 C-C, C=C, and CCl bond lengths.

 









Calc (1)
Calc (2)
Expt [2]
   







Xaa - 30.84 - 30.98 -
 31.6(8)

Xbb
  2.35
  2.44
  3.1(10)

Xcc
28.49
28.54
28.5(13)

|Xab|
39.71  *
39.74  *



|Xac|
  1.25
  1.24



|Xbc|
  0.14
  0.13



 







RMS
0.61 (2.9 %)
0.52 (2.5 %)



RSD
0.44 (1.1 %)
0.44 (1.1 %)



 
 






 








* The algabraic sign of the product XabXacXbc is positive.

 








 












Table 5.  g-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 C-C, C=C, and CCl bond lengths.
 


Point Group C1
  r (1)   r (2)





ClC(3) 1.7988 1.7956
C(3)C(2) 1.4862 1.4857
C(2)C(4) 1.3349 1.3311
ClC(3)C(2) 110.41 110.41
C(3)C(2)C(4) 122.83 122.83
ClC(3)C(2)C(4) 118.23 118.23
 

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




  r (1)   r (2)



ClC(3) 1.7891 1.7937
C(3)C(2) 1.4871 1.4866
Click on image to enlarge. C(2)C(4) 1.3338 1.3308

ClC(3)C(2) 110.59 110.59

C(3)C(2)C(4) 122.94 122.94

ClC(3)C(2)C(4) 117.32 117.32


 








 













Table 6.  g-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 21 315.8 21 365.8 21 669.09(33)

B   2 831.0   2 840.0   2 800.902(56)

C   2 743.7   2 751.9   2 713.990(55)
 
 


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 21 263.6 21 251.1 21 669.09(33)

B   2 845.8   2 843.0   2 800.902(56)

C   2 758.4   2 755.1   2 713.990(55)


 








 








[1] E.Hirota, J.Mol.Spectrosc. 35,9(1970):  Xaa = 39.42, Xbb = 3.45, and Xcc = 35.98 MHz

[2] 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.

 








 








cis-3-Chloropropene gauche-3-Bromopropene



 








 








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Last Modified 7 April 2008