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CF2Cl-C(=O)-O-CH3
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Chlorine
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Nuclear
Quadrupole Coupling Constants |
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in
gauche Methyl
Chlorodifluoroacetate |
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Calculation
of the chlorine nqcc tensors in g-CF2Cl-C(=O)-O-CH3
was made
here on molecular structures given by (1) MP2/6-311++G(d,p) and
(2) PBE1PBE/6-311+G(3d,3p) optimization.
These nqcc's are compared with the experimental values [1] in Tables 1
and 2.
Molecular structure parameters are given in Table 3, rotational
constants and dipole moments in Table 4. |
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In Tables 1 and 2, 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. ETA = (Xxx - Xyy)/Xzz.
Øz,CCl (degrees) is the angle
between the z-principal axis and the CCl bond axis. |
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RMS is the root mean square
difference between calculated and experimental diagonal nqcc's.
RSD is the residual standard
deviation
of calibration of the B1LYP/TZV(3df,2p) model for calculation of
the nqcc's. |
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Table 1. 35Cl nqcc's
in g-CF2Cl-C(=O)-O-CH3
(MHz). Calculation was made on
the (1) MP2/6-311++G(d,p) and (2)
PBE1PBE/6-311+G(3d,3p) optimized structures. |
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Calc (1) |
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Calc (2) |
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Expt [1] |
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Xaa |
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13.35 |
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12.79 |
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13.533(10) |
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Xbb |
- |
26.22 |
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27.46 |
- |
27.600(22) |
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Xcc |
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12.87 |
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14.67 |
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14.067(22) |
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Xab |
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39.58 |
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40.22 |
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38.6(40) * |
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Xac |
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23.56 |
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22.56 |
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18.2(79) * |
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Xbc |
- |
39.99 |
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38.58 |
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38.51(12) * |
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RMS |
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1.06 (5.8 %) |
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0.56 (3.0 %) |
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RSD |
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0.49 (1.1 %) |
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0.49 (1.1 %) |
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Xxx |
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38.48 |
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38.34 |
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40.0(54) |
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Xyy |
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36.67 |
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36.31 |
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32.0(79) |
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Xzz |
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75.15 |
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74.65 |
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72.0(42) |
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ETA |
- |
0.024 |
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0.027 |
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0.11(13) |
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Øz,CCl |
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1.26 |
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1.47 |
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* Absolute value. |
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Table 2. 37Cl nqcc's
in g-CF2Cl-C(=O)-O-CH3
(MHz). Calculation was made on
the (1) MP2/6-311++G(d,p) and (2)
PBE1PBE/6-311+G(3d,3p) optimized structures. |
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Calc (1) |
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Calc (2) |
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Expt [1] |
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Xaa |
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9.34 |
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8.90 |
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9.501(22) |
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Xbb |
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21.95 |
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22.55 |
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22.800(43) |
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Xcc |
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12.60 |
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13.65 |
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13.299(43) |
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|Xab| |
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32.52 |
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32.90 |
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24(10) * |
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|Xac| |
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17.86 |
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17.18 |
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27(10) * |
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|Xbc| |
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29.86 |
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28.84 |
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28.31(31) * |
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RMS |
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0.64 (4.2 %) |
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0.42 (2.8 %) |
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RSD |
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0.44 (1.1 %) |
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0.44 (1.1 %) |
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* Absolute value. |
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| Table 3. g-CF2Cl-C(=O)-O-CH3.
Selected structure parameters, (1) MP2/6-311++G(d,p)
and (2) PBE1PBE/6-311+G(3d,3p) optimized structures
(Å
and degrees). Complete structures are given
here in Z-matrix format. |
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(1) |
(2) |
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C(4)O(3) |
1.442 |
1.432 |
| O(3)C(1) |
1.330 |
1.319 |
| C(1)=O |
1.206 |
1.193 |
| C(1)C(8) |
1.540 |
1.543 |
| C(8)Cl |
1.763 |
1.768 |
| C(4)O(3)C(1) |
114.1 |
115.1 |
| O(3)C(1)=O |
127.2 |
127.1 |
| O(3)C(1)C(8) |
109.6 |
110.2 |
| C(1)C(8)Cl |
109.5 |
109.7 |
| O=C(1)C(8)Cl |
-100.4 |
-103.2 |
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| Table 4. g-CF2Cl-C(=O)-O-CH3, 35Cl species. (1) MP2/6-311++G(d,p) and (2) PBE1PBE/6-311+G(3d,3p)
optimized structures
(Å
and degrees). Rotational Constants (MHz) and B1LYP/TZV(3df,2p)
Dipole Moments (D). |
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(1) |
(2) |
Expt [1] |
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A |
2584.2 |
2603.8 |
2592.61521(74) |
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B |
1249.9 |
1257.7 |
1250.54810(37) |
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C |
1156.6 |
1153.0 |
1150.96853(34) |
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|µa| |
2.22 |
2.25 |
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|µb| |
1.73 |
1.68 |
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|µc| |
0.49 |
0.54 |
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[1] B.E.Long, R.A.Powoski, G.S.Grubbs
II, W.C.Bailey, S.A.Cooke, J.Mol.Spectrosc. 266,21(2011). |
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Table of Contents |
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Molecules/Chlorine |
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CF2ClCOOCH3.html |
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Last
Modified 29 Dec 2010 |
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