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H3C-CCl3 |
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in
Methyl Chloroform
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The complete chlorine nqcc tensor in
methyl chloroform was determined by Dore and Kisiel [1]. An ab initio equilibrium structure was
derived by Margulès et al. [2]. |
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Calculation was made here of the
chlorine nqcc's on the equilibrium structure. These are compared
with the experimental values in Tables 1 and 2. Structure
parameters and atomic coordinates are given in Tables 3 and 4,
respectively. |
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Coordinate
Systems |
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Xuu is the component of
the nqcc tensor along the threefold symmetry axis. Corresponding
to the atomic coordinates given below in Table 4, Xvv and Xww
are the components along the v- and w- axes for the Cl atom in the
uv-plane. |
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Subscripts
x,y,z refer to the principal axes of the nqcc tensor. The y-axis
is chosen coincident with the w-axis. Ø (degrees) is the
angle between its subscripted parameters. ETA = (Xxx -
Xyy)/Xzz. |
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Table 1. Chlorine nqcc's
in H3C-CCl3 (MHz). The subscripts cc, etc.
in parentheses are the axes labels of Ref. [1]. |
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Calc. |
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Expt. [1] |
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35Cl |
Xuu(cc) |
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27.47 |
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26.8907(9) |
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Xvv(aa) |
- |
66.32 |
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65.5378(12) |
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Xww(bb) |
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38.85 |
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38.6472(12) |
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Xuv(ac) |
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36.15 |
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36.510(23) |
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RMS |
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0.58 (1.3 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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39.79 |
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39.571(14) |
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Xyy |
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38.85 |
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38.6472(12) |
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Xzz |
- |
78.64 |
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78.218(14) |
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ETA |
- |
0.0119 |
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0.0118(2) |
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Øz,u |
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71.19 |
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70.846(9) |
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Øu,CCl |
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70.02 |
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Øz,CCl |
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1.17 |
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The pyramid formed by the z-principal
axes of the three Cl nqcc tensors is somewhat 'flatter' than the
molecular pyramid. This is typical of the pyramidal trichlorides. |
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Table 2. 37Cl
nqcc's in 37Cl35Cl2CCH3
(MHz). |
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Calc. |
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Expt. [1] |
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37Cl |
Xaa |
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52.91 |
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52.3028(16) |
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Xbb |
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30.62 |
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30.4585(16) |
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Xcc |
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22.29 |
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21.8443(11) |
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|Xac| |
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27.64 |
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28.032(76) |
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RMS |
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0.44 (1.3 %) |
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RSD |
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0.44 (1.1 %) |
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Xxx |
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31.36 |
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31.249(46) |
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Xyy |
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30.62 |
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30.4585(16) |
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Xzz |
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61.98 |
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61.708(46) |
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ETA |
- |
0.0119 |
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0.0128(7) |
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Øz,c |
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71.84 |
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71.45(4) |
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Øc,CCl |
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70.67 |
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Øz,CCl |
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1.17 |
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| Table 2. Molecular structure
parameters, re [2] (Å and degrees). |
| re =
CCSD(T)/V(T+d)Z + MP2/V(Q+d)Z - MP2/V(T+d)Z + core correlation |
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CCl |
1.7756 |
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CC |
1.5121 |
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CH |
1.0870 |
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CCH |
109.11 |
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CCCl |
109.98 |
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| Table 3. Atomic coordinates. |
| (More figures are shown than
are significant.) |
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u (Å) |
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v (Å) |
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w (Å) |
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Cl |
- |
0.304618 |
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1.668730 |
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0.0 |
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Cl |
- |
0.304618 |
- |
0.834365 |
± |
1.445163 |
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C |
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0.302090 |
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0.0 |
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0.0 |
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C |
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1.814190 |
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0.0 |
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0.0 |
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H |
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2.170055 |
- |
1.027097 |
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0.0 |
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H |
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2.170055 |
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0.513549 |
± |
0.889492 |
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[1] L.Dore and Z.Kisiel,
J.Mol.Spectrosc. 189,228(1998). |
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[2] L.Margulès,
M.Carvajal, and J.Demaison, J.Mol.Spectrosc. 247,160(2008). |
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CFCl3 |
SiHCl3 |
F3C-CCl3 |
OPCl3 |
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NCl3 |
PCl3 |
AsCl3 |
SPCl3 |
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CH3Cl |
CH2Cl2 |
CHCl3 |
CH3CH2Cl |
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Go back |
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Table of Contents |
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Molecules/Chlorine |
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CH3CCl3_3.html |
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Last
Modified 3 Dec 2007 |
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