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CH3OCl
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Chlorine
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Nuclear
Quadrupole Coupling Constants |
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in Methyl Hypochlorite |
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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.
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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. Ø (degrees)
is the angle between its subscripted parameters. ETA = (Xxx
- Xyy)/Xzz. |
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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. |
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Table 1. Chlorine
nqcc's in CH3OCl (MHz). Calculation was made
on the rs structure of Rigden and Butcher [1]. |
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Calc. |
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Expt. [1,2] |
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35Cl |
Xaa |
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89.41 |
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84.456(26) [2] |
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Xbb |
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29.71 |
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25.361(22) |
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Xcc |
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59.70 |
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59.095 |
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|Xab| |
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65.57 |
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68.2(13) |
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RMS |
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3.82 (6.8 %) |
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RSD |
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0.49 (1.1 %) |
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37Cl |
Xaa |
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70.75 |
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67.05 [1] |
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Xbb |
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23.70 |
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19.85 |
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Xcc |
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47.05 |
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47.20 |
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|Xab| |
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51.41 |
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RMS |
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3.09 (6.9 %) |
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RSD |
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0.44 (1.1 %) |
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Table 2. Chlorine
nqcc's in CH3OCl (MHz). Calculation was made
on the MP2/cc-pVTZ(G03) optimized molecular structure. |
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Calc. |
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Expt. [1,2] |
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35Cl |
Xaa |
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- 84.15 |
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84.456(26) [2] |
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Xbb |
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24.92 |
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25.361(22) |
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Xcc |
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59.23 |
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59.095 |
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|Xab| |
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69.03 |
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68.2(13) |
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RMS |
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0.32 (0.56 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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58.36 |
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58.0(20) |
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Xyy |
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59.23 |
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59.1 |
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Xzz |
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117.59 |
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117.1(20) |
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ETA |
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0.0074 |
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0.009(17) |
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Øz,a |
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25.84 |
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25.6(3) |
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Øa,ClO |
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26.18 |
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Øz,ClO |
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0.34 |
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37Cl |
Xaa |
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66.56 |
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67.05 [1] |
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Xbb |
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19.90 |
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19.85 |
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Xcc |
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46.66 |
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47.20 |
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|Xab| |
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54.14 |
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RMS |
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0.41 (0.92 %) |
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RSD |
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0.44 (1.1 %) |
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Table 3. Chlorine
nqcc's in CD3OCl (MHz). Calculation was made
on the MP2/cc-pVTZ(G03) optimized molecular structure. |
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Calc. |
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Expt. [2] |
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35Cl |
Xaa |
-
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79.71 |
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80.045(11) |
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Xbb |
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20.48 |
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21.072(11) |
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Xcc |
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59.23 |
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58.973 |
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|Xab| |
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72.32 |
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70(3) |
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RMS |
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0.42 (0.79 %) |
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RSD |
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0.49 (1.1 %) |
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37Cl |
Xaa |
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63.17 |
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Xbb |
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16.49 |
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Xcc |
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46.68 |
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|Xab| |
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56.75 |
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RSD |
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0.44 (1.1 %) |
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| Table 4. Molecular structure parameters, rs [1] and MP2/cc-pVTZ ropt (Å and degrees). |
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rs [1] |
ropt |
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| Z-Matrix |
ClO |
1.674(19) |
1.6948 |
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OC |
1.389(28) |
1.4255 |
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COCl |
112.8(21) |
109.11 |
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CH(1) |
1.086(18) |
1.0871 |
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CH(2,3) |
1.111(18) |
1.0891 |
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H(1)CH(2) |
110.5(18) |
109.98 |
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H(2)CH(3) |
108.3(17) |
109.94 |
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[1] J.S.Rigden and S. S.Butcher, J.Chem.Phys.
40,2109(1964).
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[2] M.Suzuki and A.Guarnieri, Z.Naturforsch. 31a,1242(1976).
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HOCl |
FClO2 |
FClO3 |
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Cl2O |
ClO2 |
ClNO3 |
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Table of Contents |
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Molecules/Chlorine |
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CH3OCl.html |
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Last modified 24 Oct 2005 |
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