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g-CF2Cl-C(=O)Cl
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in
gauche
Chlorodifluoroacetyl Chloride |
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Chlorine nqcc tensors in gauche
chlorodifluoroacetyl chloride were determined by Grubbs, et al. [1].
Calculation was made [1] of the nqcc tensors on a molecular
structure given by MP2/aug-cc-pVTZ optimization with approximate re correction of
the bond lengths. Calculated and experimental nqcc's are
compared in
Tables 1 - 4.
Structure parameters are given in Table 5, rotational constants
in Table 6. |
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In Tables 1 - 4, subscripts a,b,c
refer to the principal axes of the inertia tensor; x,y,z to the
principal axes of the nqcc tensor. Øz,CCl
(degrees) is the angle between the z-principal axis and the CCl bond
direction. ETA = (Xxx - Xyy)/Xzz. |
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RMS is the root mean square
difference between calculated and experimental diagonal nqcc's
(percentage of the average of the magnitudes of the experimental
nqcc's). RSD is the calibration residual standard deviation for
the B1LYP/TZV(3df,2p) model for calculation of the efg's/nqcc's, which
may be taken as an estimate of the uncertainty in the calculated nqcc's. |
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Table 1. Chlorine nqcc's
in g-CF235Cl(7)-C(=O)35Cl(1) (MHz).
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Calc. [1] |
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Expt. [1] |
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35Cl(1) |
Xaa |
- |
10.69 |
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11.814(15) |
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Xbb |
- |
13.42 |
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13.039(20) |
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Xcc |
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24.12 |
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24.853(12) |
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|Xab| |
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49.61 * |
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48.4(25) |
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|Xac| |
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20.24 |
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19.6(41) |
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|Xbc| |
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8.35 |
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8.90(55) |
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RMS |
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0.80 (4.8 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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42.70 |
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40.9(34) |
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Xyy |
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23.50 |
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24.4(19) |
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Xzz |
- |
66.20 |
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65.3(27) |
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ETA |
- |
0.290 |
- |
0.251(60) |
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Øz,CCl |
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1.34 |
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35Cl(7) |
Xaa |
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18.12 |
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17.485(14) |
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Xbb |
- |
22.72 |
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22.669(22) |
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Xcc |
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4.60 |
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5.184(17) |
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|Xab| |
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35.41 * |
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35.6(28) |
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|Xac| |
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24.20 |
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22.4(57) |
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|Xbc| |
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44.85 |
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44.37(39) |
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RMS |
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0.50 (3.3 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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36.30 |
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34.4(56) |
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Xyy |
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39.26 |
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40.0(38) |
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Xzz |
- |
75.56 |
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74.4(31) |
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ETA |
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0.039 |
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0.07(9) |
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Øz,CCl |
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1.62 |
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* The algebraic sign of the
product XabXacXbc is negative. |
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Table 2. Chlorine nqcc's
in g-CF237Cl(7)-C(=O)35Cl(1) (MHz).
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Calc. [1] |
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Expt. [1] |
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35Cl(1) |
Xaa |
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- 9.08 |
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10.218(24) |
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Xbb |
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14.96 |
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14.507(32) |
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Xcc |
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24.04 |
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24.725(20) |
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|Xab| |
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49.06 * |
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50.1(34) |
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|Xac| |
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21.04 |
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22.9(56) |
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|Xbc| |
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9.31 |
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10.22(91) |
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RMS |
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0.81 (4.9 %) |
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RSD |
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0.49 (1.1 %) |
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37Cl(7) |
Xaa |
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12.76 |
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12.282(25) |
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Xbb |
- |
18.58 |
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18.502(37) |
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Xcc |
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5.82 |
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6.220(27) |
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|Xab| |
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29.38 * |
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31.5(41) |
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|Xac| |
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19.11 |
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20.3(82) |
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|Xbc| |
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34.08 |
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33.86(62) |
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RMS |
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0.36 (2.9 %) |
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RSD |
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0.44 (1.1 %) |
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* The algebraic sign of the
product XabXacXbc is negative. |
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Table 3. Chlorine nqcc's
in g-CF235Cl(7)-C(=O)37Cl(1) (MHz).
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Calc. [1] |
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Expt. [1] |
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37Cl(1) |
Xaa |
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- 9.82 |
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10.684(29) |
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Xbb |
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- 9.31 |
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- 9.038(39) |
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Xcc |
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19.13 |
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19.722(25) |
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|Xab| |
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39.18 * |
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40.9(40) |
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|Xac| |
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15.86 |
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17.3(70) |
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|Xbc| |
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6.11 |
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6.6(12) |
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RMS |
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0.62 (4.7 %) |
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RSD |
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0.44 (1.1 %) |
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35Cl(7) |
Xaa |
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19.17 |
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18.534(29) |
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Xbb |
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23.62 |
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23.575(41) |
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Xcc |
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4.45 |
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5.041(29) |
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|Xab| |
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34.76 * |
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34.0(65) |
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|Xac| |
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23.60 |
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23(12) |
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|Xbc| |
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45.24 |
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44.62(99) |
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RMS |
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0.50 (3.2 %) |
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RSD |
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0.49 (1.1 %) |
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* The algebraic sign of the
product XabXacXbc is negative. |
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Table 4. Chlorine nqcc's
in g-CF237Cl(7)-C(=O)37Cl(1) (MHz).
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Calc. [1] |
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Expt. [1] |
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37Cl(1) |
Xaa |
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- 8.58 |
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- 9.454(70) |
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Xbb |
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10.50 |
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10.171(84) |
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Xcc |
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19.09 |
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19.625(45) |
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|Xab| |
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38.80 * |
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|Xac| |
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16.50 |
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|Xbc| |
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6.84 |
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RMS |
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0.62 (4.7 %) |
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RSD |
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0.44 (1.1 %) |
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37Cl(7) |
Xaa |
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13.66 |
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13.175(66) |
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Xbb |
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19.36 |
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19.272(79) |
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Xcc |
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5.70 |
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6.097(43) |
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|Xab| |
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28.86 * |
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|Xac| |
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18.64 |
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|Xbc| |
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34.41 |
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RMS |
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0.36 (2.8 %) |
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RSD |
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0.44 (1.1 %) |
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* The algebraic sign of the
product XabXacXbc is negative. |
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| Table 5. g-CF2Cl-C(=O)Cl.
Structure parameters, MP2/aug-cc-pVTZ optimization with
approximate re bond lengths [2] (Å and
degrees). This structure is given
here in Z-matrix
format. |
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Cl(1)C(2) |
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1.7448 |
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C(2)O(3) |
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1.1818 |
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C(2)C(4) |
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1.5423 |
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C(4)F(5) |
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1.3320 |
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C(4)F(6) |
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1.3265 |
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C(4)Cl(7) |
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1.7558 |
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Cl(1)C(2)O(3) |
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124.45 |
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Cl(1)C(2)C(4) |
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112.22 |
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C(2)C(4)F(5) |
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110.71 |
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C(2)C(4)F(6) |
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109.02 |
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C(2)C(4)Cl(7) |
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108.92 |
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O(3)Cl(1)C(2)C(4) |
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179.02 |
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Cl(1)C(2)C(4)F(5) |
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- 47.30 |
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Cl(1)C(2)C(4)F(6) |
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166.33 |
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Cl(1)C(2)C(4)Cl(7) |
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73.76 |
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| Table 6. g-CF235Cl-C(=O)35Cl.
Rotational constants (MHz). |
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Calc. [1] |
Expt. [1] |
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A |
2424.9 |
2422.40712(62) |
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B |
1470.0 |
1454.03317(51) |
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C |
1280.3 |
1266.67027(65) |
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[1] G.S.Grubbs III, C.T.Dewberry,
A.King, W.Lin, W.C.Bailey, and S.A.Cooke, J.Mol.Spectrosc.
263,127(2010). |
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Table of Contents |
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Molecules/Chlorine |
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CF2ClCOCl.html |
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Last
Modified 1 June 2010 |
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