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H2C=CHBr
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Bromine |
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Nuclear
Quadrupole Coupling Constants |
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in Vinyl Bromide |
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Hayashi et al. [1] determined the
bromine nqcc's in vinyl bromide and derived a substitution molecular
structure. Calculation of the nqcc's was made on this structure.
These are compared with the experimental nqcc's in Table 1.
Structure parameters are given in Table 2. |
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Zvereva-Loëte, et al. [2] have
recently published several vinyl bromide structures. A summary of
calculations made on these structures is given in Table 3. |
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In Table 1, 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 c-axis. Ø
(degrees) is the angle between its subscripted parameters. ETA = (Xxx - Xyy)/Xzz. |
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RMS is the root measn square
difference between calculated and experimental diagonal nqcc's. RSD
is the residual standard deviation of the calibration of the B1LYP/TZV(3df,3p) model for calculation of the nqcc's. |
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Table 1. Bromine nqcc's
in H2C=CHBr (MHz). |
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Calc. |
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Expt. [1] |
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79Br |
Xaa |
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472.53 |
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470.98(9) |
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Xbb |
- |
220.08 |
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216.97 |
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Xcc |
- |
252.45 |
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254.01(10) |
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|Xab| |
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247.81 |
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246.14(564) |
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RMS |
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2.20 (0.70 %) |
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RSD |
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1.58 (0.39 %) |
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Xxx |
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299.61 |
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295.97(328) |
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Xyy |
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252.45 |
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254.01(10) |
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Xzz |
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552.06 |
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549.97(328) |
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ETA |
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0.085 |
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0.0763 |
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Øz,a |
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17.79 |
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17.78 |
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Øa,CBr |
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17.44 |
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17.43 |
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Øz,CBr |
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0.35 |
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0.35 |
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81Br |
Xaa |
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394.94 |
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393.58(7) |
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Xbb |
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184.02 |
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181.36 |
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Xcc |
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210.92 |
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212.22 |
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|Xab| |
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206.83 |
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204.17(506) |
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RMS |
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1.88 (0.71 %) |
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RSD |
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1.38 (0.40 %) |
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| Table 2. Structure parameters, rs [1] (Å and degrees/minutes). |
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CBr |
1.884 |
| CC |
1.332 |
| CH |
1.080 |
| CHt |
1.080 (assumed) |
| CHc |
1.088 |
| CCBr |
122o35' |
| CCH |
123o40' |
| CCHt |
119o15' |
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CCHc |
121o17' |
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Table 3. 79Br
nqcc's in CH2CHBr (MHz). Calculation was made on the molecular structures (column 1) of Zvereva-Loëte, et al. [2]. RMS (column 5) is
the root mean square difference between calculated and
experimental
diagonal nqcc's [1]. |
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Structure |
Xaa |
Xbb |
Xcc |
RMS |
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ro |
473.40 |
-220.60 |
-252.79 |
2.62 |
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rm(1) |
471.92 |
-220.52 |
-251.40 |
2.60 |
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rm(2) mod |
471.72 |
-220.81 |
-250.91 |
2.88 |
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rm(1L) |
472.03 |
-220.60 |
-251.43 |
2.64 |
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rs-fit + com |
473.15 |
-220.58 |
-252.57 |
2.57 |
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re |
471.74 |
-220.74 |
-251.00 |
2.82 |
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ab initio * |
472.62 |
-221.46 |
-251.16 |
3.21 |
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expt. nqcc's |
470.98(9) |
-216.97 |
-254.01(10) |
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* CCSD(T)/cc-pVQZ-offset. |
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[1] M.Hayashi, C.Ikeda and T.Inagusa, J.Mol.Spectrosc. 139,299 (1990). |
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[2] N.Zvereva-Loëte, J.Demaison, and H.D.Rudolph, J.Mol.Spectrosc. 236,248(2006). |
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H2C=CFBr |
c-BrHC=CHF |
t-BrHC=CHF |
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H2C=CHCl |
c-ClHC=CHF |
t-ClHC=CHF |
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Table of Contents |
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Molecules/Bromine |
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CH2CHBr.html |
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Last
Modified 21 March 2006 |
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