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CH2Br-CH=CH2
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Bromine |
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Nuclear
Quadrupole Coupling Constants |
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in gauche-3-Bromopropene
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(Allyl Bromide)
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Bromine nqcc's
in g-3-bromopropene were first determined in 1976 by Niide et al. [1],
and subsequently redetermined in 2014 by McCabe and Shipman [2].
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Calculation of the nqcc tensor
was made here on molecular structures given by MP2/aug-cc-pVTZ(G03) and
MP2/6-311+G(3df,3pd) optimizations; and on these
same structures but with empirically corrected C-C, C=C, and CBr bond
lengths. These calculated nqcc's are compared
with the experimental values [2] 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,CBr
(degrees) is the angle between the z-principal axis and the CBr 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 of
the B1LYP/TZV(3df,p) model for calculation of the nqcc's. |
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Table 1. 79Br
nqcc's in g-3-Bromopropene (MHz). |
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Calc (1) was made on the
MP2/aug-cc-pVTZ(G03) optimized molecular structure. |
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Calc (2) was made on this same
structure but with empirically corrected C-C, C=C, and CBr bond lengths. |
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Calc (1) |
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Calc (2) |
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Expt. [2] |
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Xaa |
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349.05 |
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351.11 |
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349.4(13) |
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Xbb |
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- 73.42 |
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- 74.69 |
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- 72.8(27) |
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Xcc |
- |
275.64 |
- |
276.42 |
- |
276.6(10) |
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|Xab| |
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362.55 * |
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362.83 |
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363(10) |
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|Xac| |
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13.92 |
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13.78 |
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|Xbc| |
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15.85 |
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15.61 |
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RMS |
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0.69 (0.30 %) |
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1.47 (0.63 %) |
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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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Xxx |
- |
286.32 |
- |
286.94 |
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Xyy |
- |
271.57 |
- |
272.42 |
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Xzz |
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557.89 |
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559.36 |
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ETA |
- |
0.026 |
- |
0.026 |
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Øz,CBr |
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0.39 |
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0.39 |
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* The algabraic sign of the product XabXacXbc is
positive. |
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Table 2. 81Br
nqcc's in g-3-Bromopropene (MHz). |
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Calc (1) was made on the
MP2/aug-cc-pVTZ(G03) optimized molecular structure. |
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Calc (2) was made on this same
structure but with empirically corrected C-C, C=C, and CBr bond lengths. |
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Calc (1) |
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Calc (2) |
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Expt. [2] |
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Xaa |
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292.10 |
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293.82 |
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292.5(13) |
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Xbb |
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- 61.83 |
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- 62.89 |
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- 61.3(11)
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Xcc |
- |
230.27 |
- |
230.93 |
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231.1(1) |
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|Xab| |
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302.61 * |
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302.85 * |
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303(11) |
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|Xac| |
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11.81 |
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11.70 |
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|Xbc| |
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13.33 |
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13.13 |
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RMS |
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0.61 (0.31 %) |
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1.12 (0.61 %) |
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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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* The algabraic sign of the product XabXacXbc is
positive. |
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Table 3. 79Br
nqcc's in g-3-Bromopropene (MHz). |
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Calc (1) was made on the
MP2/6-311+G(3df,3pd) optimized molecular structure. |
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Calc (2) was made on this same
structure but with empirically corrected C-C, C=C, and CBr bond lengths. |
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Calc (1) |
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Calc (2) |
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Expt. [2] |
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Xaa |
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349.20 |
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350.15 |
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349.4(13) |
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Xbb |
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- 73.34 |
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- 73.93 |
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- 72.8(27) |
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Xcc |
- |
275.86 |
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276.22 |
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276.6(10) |
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|Xab| |
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363.99 |
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364.07 |
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363(10) |
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|Xac| |
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20.14 |
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19.89 |
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|Xbc| |
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19.26 |
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19.02 |
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RMS |
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0.54 (0.23 %) |
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0.81 (0.35 %) |
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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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Xxx |
- |
287.16 |
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287.40 |
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Xyy |
- |
272.51 |
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272.88 |
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Xzz |
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559.67 |
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560.28 |
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ETA |
- |
0.0262 |
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0.0259 |
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Øz,CBr |
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0.42 |
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0.42 |
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* The algabraic sign of the product XabXacXbc is
positive. |
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Table 4. 81Br
nqcc's in g-3-Bromopropene (MHz). |
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Calc (1) was made on the
MP2/6-311+G(3df,3pd) optimized molecular structure. |
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Calc (2) was made on this same
structure but with empirically corrected C-C, C=C, and CBr bond lengths. |
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Calc (1) |
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Calc (2) |
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Expt. [2] |
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Xaa |
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292.23 |
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293.02 |
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292.5(13) |
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Xbb |
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- 61.77 |
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- 62.26 |
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- 61.3(11) |
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Xcc |
- |
230.46 |
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230.76 |
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231.1(1) |
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|Xab| |
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303.81 |
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303.88 |
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303(11) |
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|Xac| |
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16.99 |
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16.78 |
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|Xbc| |
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16.16 |
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15.96 |
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RMS |
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0.48 (0.25 %) |
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0.66 (0.34 %) |
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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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* The algabraic sign of the product XabXacXbc is
positive. |
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| Table 5.
g-3-Bromopropene. Heavy atom structure parameters (Å and degrees).
Complete structures are given here
in Z.matrix format. |
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r (1) = MP2/aug-cc-pVTZ(G03)
opt. |
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r (2) = r (1) but with corrected C-C, C=C, and CBr bond lengths. |
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| Point Group C1 |
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r (1) |
r (2) |
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BrC(3) |
1.9467 |
1.9546 |
| C(3)C(2) |
1.4832 |
1.4828 |
| C(2)C(4) |
1.3354 |
1.3316 |
| BrC(3)C(2) |
110.30 |
110.30 |
| C(3)C(2)C(4) |
122.88 |
122.88 |
| BrC(3)C(2)C(4) |
116.40 |
116.40 |
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| r (1) = MP2/6-311+G(3df,3pd)
opt. |
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CBr bond lengths. |
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r (1) |
r (2) |
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| BrC(3) |
1.9527 |
1.9562 |
| C(3)C(2) |
1.4839 |
1.4836 |
| Click on image to enlarge. |
C(2)C(4) |
1.3347 |
1.3316 |
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BrC(3)C(2) |
110.43 |
110.43 |
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C(3)C(2)C(4) |
122.96 |
122.96 |
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BrC(3)C(2)C(4) |
115.17 |
115.17 |
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| Table 6.
g-3-Bromopropene. Rotational constants (MHz). 79Br
species. |
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r (1) = MP2/aug-cc-pVTZ(G03)
opt. |
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r (2) = r (1) but with
corrected C-C, C=C, and CBr bond lengths. |
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r (1) |
r (2) |
Expt. [2] |
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A |
19 273.8 |
19 256.4 |
19 247.18(21) |
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B |
2 001.2 |
1 995.4 |
1 975.340(19) |
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C |
1 941.0 |
1 935.1 |
1 914.843(17) |
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r (1) = MP2/6-311+G(3df,3pd)
opt. |
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r (2) = r (1) but with
corrected C-C, C=C, and CBr bond length. |
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r (1) |
r (2) |
Expt. [2] |
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A |
19 056.6 |
19 058.6 |
19 247.18(21) |
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B |
1 999.6 |
1 997.9 |
1 975.340(19) |
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C |
1 938.0 |
1 936.2 |
1 914.843(17) |
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[1] Y.Niide, M.Takano, T.Satoh, and
Y.Sasada, J.Mol.Spectrosc. 63,108(1976): For 79Br, Xaa = 348.2(46), Xbb = -71.9(27), Xcc = -276.3(53), |Xab| = 358.7(54) MHz; and for 81Br; and Xaa = 283.2(49), Xbb = -55.6(29), Xcc = -227.6(57), |Xab| = 296.0(68) MHz.
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[2] M.McCabe and S.Shipman, Abstract RE09, 69th International
Symposium on Molecular Spectroscopy, Champaign-Urbana, Ill. 2014. |
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cis-3-Chloropropene |
gauche-3-Chloropropene
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Table of Contents |
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Molecules/Bromine |
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gCH2BrCHCH2.html |
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Last
Modified 30 July 2014 |
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