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CF2Cl-C(=O)-CF3 |
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in
Chloropentafluoroacetone
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Calculations of the chlorine nqcc's
in chloropentafluoroacetone were made on structures given by
MP2/6-311+G(3df) optimization with
approximate re C-C, CF, and
C=O, and CCl
bond lengths and by MP2/aug-cc-pVTZ
optimization with approximate re
C-C, CF, and
C=O, and CCl
bond lengths. These
calculated nqcc's are compared with experimental values [1] in Tables 1
and 2. Structure
parameters are given in Table 3, rotational constants 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; 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.
Øz,CCl (degrees) is the angle between the z-principal
axis and the CCl axis. ETA = (Xxx - Xyy)/Xzz. |
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RMS is the root mean square
difference between calculated and experimental diagonal nqcc's (percent
of the average of the magnitudes of experimental nqcc's). RSD is
the residual standard deviation of the model for calculation of the
nqcc's, which may be taken as an estimate of uncertainty in the
calculated nqcc's (not taking into account inaccuracies in the
structure parameters). |
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Table 1. 35Cl
nqcc's in CF2Cl-C(=O)-CF3 (MHz).
Calculation was made on structures given by (1) MP2/6-311+G(3df)
optimization and (2) MP2/aug-cc-pVTZ optimization, each with
approximate re bond lengths. |
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Calc (1) |
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Calc (2) |
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Expt [1] |
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35Cl |
Xaa |
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12.08 |
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12.99 |
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13.206(24) |
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Xbb |
- |
12.93 |
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14.50 |
- |
15.011(32) |
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Xcc |
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0.84 |
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1.50 |
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1.805(21) |
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Xab |
- |
36.48 |
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36.29 |
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32.6(70) |
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Xac |
- |
28.93 |
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27.97 |
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31.8(72) |
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Xbc |
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43.97 |
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44.15 |
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43.89(57) |
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RMS |
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1.47 (15 %) |
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0.36 (3.6 %) |
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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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35.93 |
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35.79 |
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34(7) |
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Xyy |
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39.39 |
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39.36 |
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40(7) |
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Xzz |
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75.32 |
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75.15 |
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75(6) |
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ETA |
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0.0460 |
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0.0474 |
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0.1(1) |
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Øz,CCl |
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1.70 |
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1.74 |
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Table 2. 37Cl
nqcc's in CF2Cl-C(=O)-CF3 (MHz).
Calculation was made on structures given by (1) MP2/6-311+G(3df)
optimization and (2) MP2/aug-cc-pVTZ optimization, each with
approximate re bond lengths. |
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Calc (1) |
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Calc (2) |
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Expt [1] |
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37Cl |
Xaa |
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8.49 |
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9.22 |
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9.413(37) |
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Xbb |
- |
13.03 |
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14.17 |
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14.430(49) |
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Xcc |
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4.54 |
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4.94 |
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5.017(32) |
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Xab |
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30.40 |
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30.20 |
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34.0(97) |
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Xac |
- |
21.71 |
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21.02 |
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16(21) |
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Xbc |
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33.43 |
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33.52 |
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33.0(11) |
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RMS |
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1.00 (10 %) |
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0.19 (2.0 %) |
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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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Xxx |
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28.32 |
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28.21 |
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Xyy |
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31.04 |
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31.02 |
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Xzz |
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59.36 |
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59.22 |
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ETA |
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0.0460 |
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0.0474 |
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Øz,CCl |
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1.70 |
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1.74 |
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| Table 3. CF2Cl-C(=O)-CF3.
Selected structure parameters (Å and degrees).
r(1) = MP2/6-311+G(3df)
optimization and r(2) = MP2/aug-cc-pVTZ optimization, each with
approximate re bond lengths.
Complete
structures are given here in Z-matrix
format. |
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| Point Group C1 |
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r(1) |
r(2) |
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C(1)O |
1.1943 |
1.1945 |
| C(1)C(3) |
1.5441 |
1.5441 |
| C(1)C(4) |
1.5402 |
1.5394 |
| C(4)Cl |
1.7574 |
1.7574 |
| C(3)C(1)C(4) |
116.55 |
116.72 |
| C(3)C(1)O |
121.78 |
121.65 |
| C(4)C(1)O |
121.67 |
121.62 |
| C(1)C(4)Cl |
108.72 |
108.49 |
| ClC(4)C(1)O |
91.68 |
92.48 |
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| Table 4. CF235Cl-C(=O)-CF3.
Rotational Constants (MHz).
r(1) = MP2/6-311+G(3df)
optimization and r(2) = MP2/aug-cc-pVTZ optimization, each with
approximate re bond lengths. |
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r(3) |
r(4) |
Expt [1] |
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A |
1777.7 |
1776.9 |
1770.54709(61) |
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B |
861.3 |
862.6 |
852.96221(45) |
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C |
826.6 |
826.5 |
816.40819(59) |
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[1] G.Kadiwar, C.T.Dewberry,
G.S.Grubbs II, and S.A.Cooke, Abstract RH11, 65th OSU International
Symposium on Molecular Spectroscopy, 2010. |
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CF2Cl-C(=O)-CF2Cl |
CH2Cl-C(=O)-CH2Cl |
CH2Cl-C(=O)-CH3 |
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Table of Contents |
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Molecules/Chlorine |
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CF2ClCOCF3.html |
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Last
Modified 10 July 2010 |
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