HCC-CH2Cl



































 









Chlorine


Nuclear Quadrupole Coupling Constants


in Propargyl Chloride


 








 








Calculation of the chlorine nqcc tensors was made here on structures given by MP2/aug-cc-pVTZ(G03) optimization (ropt), and on this optimized structure but with corrected CCl, C-C, and triple CC bond lengths (~ re, see here).  These nqcc's are compared with the experimental values [1] in Tables 1 and 2.  Structure parameters are given in Table 3, rotational constants in Table 4.

 








In Tables 1 and 2, 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.

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 nqcc's, which may be taken as an estimate ofthe uncertainty in the calculated nqcc's.

 








  








   







Table 1.  35Cl nqcc's in HCC-CH2Cl (MHz).  Calculation was made on the (1) ropt and (2) ~ re structures.

 









Calc (1)
Calc (2)
Expt. [1]
   







Xaa - 31.78 - 31.76 - 30.4

Xbb
- 7.41
- 7.35
- 7.5

Xcc
39.19
39.11
37.9

|Xab|
56.79
56.68



 







RMS
1.1 (4.3 %)
1.1 (4.2 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
38.49
38.42



Xyy
39.19
39.11



Xzz - 77.68 - 77.54



ETA
0.009
0.009



Øz,a
38.95
38.92



Øa,CCl
39.30
39.27



Øz,CCl
  0.35
  0.34



 







   








 








   







Table 2.   37Cl nqcc's in HCC-CH2Cl (MHz).  Calculation was made on the (1) ropt and (2) ~ re structures.

 









Calc (1)
Calc (2)
Expt.
   







Xaa - 25.47 - 25.46



Xbb
- 5.42
- 5.36



Xcc
30.89
30.83



|Xab|
44.66
44.58



 







RSD
0.44 (1.1 %)
0.44 (1.1 %)



 








 








 












Table 3.  HCC-CH2Cl.  Molecular structure parameters, ropt and ~ re (Å and degrees).   These structures are given here in Z-matrix format.
 




  ropt  ~ re





ClC(2) 1.7932 1.7900
C(2)H(6,7) 1.0867 1.0867
C(2)C(3) 1.4499 1.4510
C(3)C(4) 1.2147 1.2040
C(4)H 1.0619 1.0619
ClC(2)C(3) 111.37 111.37
Click on C(2)C(3)C(4) 179.52 179.52
image to enlarge. C(3)C(4)H 179.84 179.84
CCCH angles are C(3)C(2)H(6,7) 111.20 111.20
exaggerated. H(6)C(2)H(7) 109.39 109.39


 








 













Table 4.  HCC-CH2Cl.  Rotational constants (MHz).  35Cl species.
 



 
   ropt    ~ re    Expt. [1]






A 24 074.0 24 184.7 24 299.28(50)

B   3 086.1   3 100.0   3 079.77(20)

C   2 783.2   2 796.0   2 777.73(20)


 








 








[1] E.Hirota, T.Oka, and Y.Morino, J.Chem.Phys. 28,444(1958); E.Hirota, and Y.Morino, Bull.Chem.Soc.Jpn. 34,341(1961).

 








 








HCC-CH2I HCC-CH2Br HCC-CH2CN CH3Cl

 








 








Table of Contents




Molecules/Chlorine




 








 













HCCCH2Cl.html






Last Modified 13 March 2008