CH3OCl















 






 








Chlorine


Nuclear Quadrupole Coupling Constants


in Methyl Hypochlorite


 








 


















Calculation of the chlorine nqcc's in methyl hypochloride was made on the substitution structure of Rigden and Butcher [1], and on the structure obtained by MP2/cc-pVTZ optimization.  These nqcc's are compared with the experimental values [1,2] in Tables 1 - 3.  Structure parameters are given in Table 4.


 








In Tables 1 - 3, 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 c-axis, these are perpendicular to the plane of the molecule.  (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 (percent of average magnitude of experimental nqcc's).  RSD is the residual standard deviation of calibration of the B1LYP/TZV(3df,2p) model for calculation of the Cl nqcc's.

 








 








   







Table 1. Chlorine nqcc's in CH3OCl (MHz).  Calculation was made on the rs structure of Rigden and Butcher [1].
   










Calc.
Expt. [1,2]
   







35Cl Xaa - 89.41 - 84.456(26)  [2]


Xbb
29.71
25.361(22)


Xcc
59.70
59.095


|Xab|
65.57
68.2(13)

 







RMS
3.82 (6.8 %)




RSD
0.49 (1.1 %)



 






37Cl Xaa - 70.75 - 67.05   [1]


Xbb
23.70
19.85


Xcc
47.05
47.20


|Xab|
51.41



 







RMS
3.09 (6.9 %)




RSD
0.44 (1.1 %)



 






   








 








   







Table 2. Chlorine nqcc's in CH3OCl (MHz).  Calculation was made on the MP2/cc-pVTZ(G03) optimized molecular structure.
   










  Calc.
Expt. [1,2]
   







35Cl Xaa
- 84.15 - 84.456(26)  [2]


Xbb
  24.92
25.361(22)


Xcc
  59.23
59.095


|Xab|
  69.03
68.2(13)

 







RMS
0.32 (0.56 %)



RSD
0.49 (1.1 %)



 







Xxx
  58.36
  58.0(20)


Xyy
  59.23
  59.1


Xzz - 117.59 - 117.1(20)


ETA
0.0074
0.009(17)


z,a
25.84
25.6(3)


a,ClO
26.18




z,ClO
  0.34



 






37Cl Xaa - 66.56 - 67.05   [1]


Xbb
19.90
19.85


Xcc
46.66
47.20


|Xab|
54.14



 







RMS
0.41 (0.92 %)



RSD
0.44 (1.1 %)



 







 








 








   







Table 3. Chlorine nqcc's in CD3OCl (MHz).  Calculation was made on the MP2/cc-pVTZ(G03) optimized molecular structure.
   










  Calc.
Expt. [2]
   







35Cl Xaa -
79.71 - 80.045(11)


Xbb
20.48
21.072(11)


Xcc
59.23
58.973


|Xab|
72.32
70(3)

 







RMS
0.42 (0.79 %)



RSD
0.49 (1.1 %)



 






37Cl Xaa - 63.17




Xbb
16.49




Xcc
46.68




|Xab|
56.75



 







RSD
0.44 (1.1 %)



 







 









 




Table 4. Molecular structure parameters, rs [1] and MP2/cc-pVTZ ropt ( and degrees).
 






   rs [1]   ropt





Z-Matrix ClO 1.674(19) 1.6948


OC 1.389(28) 1.4255


COCl 112.8(21) 109.11


CH(1) 1.086(18) 1.0871


CH(2,3) 1.111(18) 1.0891


H(1)CH(2) 110.5(18) 109.98


H(2)CH(3) 108.3(17) 109.94


 








 








[1] J.S.Rigden and S. S.Butcher, J.Chem.Phys. 40,2109(1964).

[2] M.Suzuki and A.Guarnieri, Z.Naturforsch. 31a,1242(1976).

 








 








HOCl FClO2 FClO3


Cl2O ClO2 ClNO3



 








 








Table of Contents




Molecules/Chlorine




 








 













CH3OCl.html






Last modified 24 Oct 2005