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CHF2Br |
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Bromine |
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Nuclear
Quadrupole Coupling Constants |
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in
Bromodifluoromethane |
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Bromine nqcc's in
bromodifluoromethane were determined by Ogata et al. [1], who also
derived an effective ro molecular structure.
Calculation
of the nqcc's was made here on this structure, on an ~re structure given by
MP2/aug-cc-pVTZ optimization with empirically corrected CBr, CCl, and
CF bond lengths, and on an ab
initio (a.i.) re structure derived by Charmet et al.
[2] by CCSD(T) method in conjunction with a hierarchical series of
correlation consistent bases extrapolated to CBS. Calculated and
experimental nqcc's are
compared in Tables 1 and 2.
Structure parameters are given in Table 5. |
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In Tables 3 and 4, the results are
shown of calculation on a CCSD(T)/cc-pCVQZ ab initio structure derived by
Cazzoli et al. [3]. Also shown in these Tables are the results of
calculation of the nqcc's made at the CCSD(T)/cc-pCVQZ level of theory
with relativistic and vibrational corrections [3]. These are
compared with the experimental nqcc's of Cazzoli et al. [3]. |
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In Tables 1 - 4, the
subscripts
a,b,c refer to the principal axes of the inertia tensor. Subscripts
x,y,z refer to the principal axes of the nqcc tensor.
The nqcc y-axis is chosen coincident with the b-axis. These are
perpendicular to the symmetry 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
(percentage of average of absolute experimental nqcc's).
RSD
is the residual standard deviation of the calibration of the
computional model for calculation of the nqcc's, which may be
taken as
an estimate of the uncertainty in the calculated nqcc's. |
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Table 1. 79Br nqcc's in CHF2Br
(MHz). Calculation was made on ro, ~re,
and a.i. re [2] structures. |
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Calc / ro |
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Calc / ~re |
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Calc / a.i. re |
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Expt. [1] |
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Xaa |
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530.28 |
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523.75 |
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524.54 |
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521.28(9) |
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Xbb |
- |
282.62 |
- |
280.32 |
- |
280.78 |
- |
279.80(6) |
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Xcc |
- |
247.66 |
- |
243.43 |
- |
243.76 |
- |
241.48 |
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|Xac| |
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183.87 |
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183.02 |
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182.77 |
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187.1(26) |
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RMS |
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6.58 (1.9 %) |
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1.84 (0.53 %) |
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2.37 (0.68 %) |
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RSD |
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1.58 (0.39 %) |
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1.58 (0.39 %) |
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1.58 (0.39 %) |
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Xxx |
- |
288.93 |
- |
284.86 |
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285.02 |
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284.9(23) |
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Xyy |
- |
282.62 |
- |
280.32 |
- |
280.78 |
- |
279.80(6) |
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Xzz |
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571.55 |
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565.18 |
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565.80 |
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564.7(23) |
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ETA |
- |
0.011 |
- |
0.0080 |
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0.0075 |
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0.009(4) |
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Øz,a |
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12.6 |
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12.75 |
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12.72 |
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13.1(3) |
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Øa,CBr |
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12.5 |
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12.48 |
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12.46 |
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Øz,CBr |
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0.1 |
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0.27 |
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0.26 |
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Table 2. 81Br nqcc's in CHF2Br
(MHz). Calculation was made on ro, ~re, and
a.i. re [2] structures. |
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Calc / ro |
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Calc / ~re |
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Calc / a.i. re |
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Expt. [1] |
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Xaa |
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443.09 |
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437.64 |
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438.30 |
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435.61(10) |
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Xbb |
- |
236.12 |
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234.20 |
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234.58 |
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233.84(6) |
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Xcc |
- |
206.97 |
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203.44 |
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203.71 |
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201.76 |
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|Xac| |
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153.49 |
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152.79 |
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152.57 |
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148.5(29) |
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RMS |
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5.42 (1.9 %) |
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1.53 (0.53 %) |
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1.96 (0.68 %) |
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RSD |
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1.38 (0.40 %) |
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1.38 (0.40 %) |
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1.38 (0.40 %) |
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Xxx |
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241.39 |
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237.99 |
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238.13 |
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234.6(25) |
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Xyy |
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236.12 |
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234.20 |
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234.58 |
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233.84(6) |
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Xzz |
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477.51 |
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472.19 |
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472.71 |
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468.5(25) |
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ETA |
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0.011 |
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0.0080 |
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0.0075 |
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0.002(5) |
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Øz,a |
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12.6 |
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12.74 |
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12.71 |
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12.5(4) |
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Øa,CBr |
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12.5 |
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12.47 |
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12.45 |
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Øz,CBr |
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0.1 |
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0.27 |
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0.26 |
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Table 3. 79Br nqcc's in CHF2Br
(MHz). Calculation was made on the a.i. re [3]
structure. |
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Calc |
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Calc [3] |
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Expt. [3] |
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79Br |
Xaa |
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522.94 |
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521.353 |
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521.257(9) |
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Xbb |
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279.68 |
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279.659 |
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279.804(40) |
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Xcc |
- |
243.27 |
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241.694 |
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241.453(40) |
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|Xac| |
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181.57 |
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183.963 |
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185.87(28) |
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RMS |
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1.43 (0.41 %) |
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0.172 (0.05 %) |
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RSD |
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1.58 (0.39 %) |
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Xxx |
- |
284.11 |
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Xyy |
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279.68 |
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Xzz |
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563.79 |
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ETA |
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0.0079 |
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Øz,a |
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12.68 |
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Øa,CBr |
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12.45 |
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Øz,CBr |
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0.23 |
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Table 4. 81Br nqcc's in CHF2Br
(MHz). Calculation was made on the a.i. re [3]
structure. |
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Calc |
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Calc [3] |
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Expt. [3] |
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81Br |
Xaa |
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436.96 |
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435.628 |
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435.521(10) |
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Xbb |
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233.66 |
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233.644 |
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233.701(32) |
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Xcc |
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203.30 |
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201.984 |
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201.820(32) |
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|Xac| |
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151.57 |
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153.567 |
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155.210(89) |
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RMS |
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1.19 (0.41 %) |
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0.118 (0.04 %) |
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RSD |
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1.58 (0.39 %) |
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Xxx |
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237.37 |
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Xyy |
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233.66 |
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Xzz |
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471.03 |
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ETA |
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0.0079 |
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Øz,a |
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12.67 |
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Øa,CBr |
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12.44 |
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Øz,CBr |
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0.23 |
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| Table 5. CHF2Br
Structure parameters, ro [2], ~re,
and a.i. re [2,3] (Å
and degrees). |
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ro |
~re |
a.i.
re [2] |
a.i. re
[3] |
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| CBr |
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1.908(15) |
1.9258 |
1.9355 |
1.9275 |
| CF |
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1.347(11) |
1.3359 |
1.3358 |
1.3343 |
| CH |
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1.098 |
1.0849 |
1.0854 |
1.0842 |
| BrCH |
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110.8 |
109.02 |
108.44 |
108.60 |
| BrCF |
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110.6(8) |
109.77 |
109.55 |
109.71 |
| FCF |
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107.4(1) |
108.22 |
108.45 |
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110.21 |
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| Z-Matrix |
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| H |
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| C |
1 |
R2 |
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| Br |
2 |
R3 |
1 |
A3 |
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| F |
2 |
R4 |
3 |
A4 |
1 |
D |
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| F |
2 |
R4 |
3 |
A4 |
1 |
- D |
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ro |
~re |
a.i. re
[2] |
a.i. re
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| R2 = 1.098 |
1.0849 |
1.0854 |
1.0842 |
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| R3 = 1.908 |
1.9258 |
1.9355 |
1.9275 |
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| R4 = 1.347 |
1.3359 |
1.3358 |
1.3343 |
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| A3 = 110.8 |
109.024 |
108.44 |
108.60 |
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| A4 = 110.6 |
109.7735 |
109.55 |
109.71 |
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| D = 120.5735 |
120.4292 |
120.5765 |
120.51401 |
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[1] T.Ogata, S.Kuwano, and S.Oe,
J.Mol.Spectrosc. 185,147(1997). |
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[2] A.P.Charmet, P.Stoppa,
N.Tasinato, A.Baldan, S.Giorgianni, and A.Gambi, J.Chem.Phys.
133,044310(2010). |
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[3] G.Cazzoli, L.Cludi, C.Puzzarini,
P.Stoppa, A.Pietropolloi Charmet, N.Tasinato, A.Baldacci, A.Baldan,
S.Giorgianni, R.Wugt Larsen, S.Stopkowicz, and J.Gauss, J.Physical
Chemistry A, 115,453(2011). |
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BrClCF2 |
CH3Cl |
CH3Br |
CF2Cl2 |
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CHF2Cl |
CF3Cl |
CF3Br |
CH2Cl2 |
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CH2FCl |
CH2Br2 |
BrClCH2 |
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Table of Contents |
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Molecules/Bromine |
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CHBrF2.html |
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Last
Modified 27 Dec 2010 |
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