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C5H9Br |
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Bromine |
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Nuclear
Quadrupole Coupling Constants |
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in
Bromocyclopentane
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Calculation of bromine
nuclear quadrupole coupling constant tensors in bromocyclopentane was made here on ropt
molecular
structures given by PBE1PBE/6-31G(3d,3p) and M06-2X/6-31G(3d,3p)
optimization (assuming Cs symmetry) of each of the axial and
equatorial conformers shown below:
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axial
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equatorial |
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Calculated
and experimental [1] nqcc's are compared in Tables 1 and 2, rotational
constants are compared in Table 3. Structure parameters are given
here in Z-matrix format.
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In Tables 1 and 2, subscripts a,b,c
refer to the
principal axes of the inertia tensor; subscripts x,y,z to the principal
axes
of the nqcc tensor.
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'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,3p) model for calculation of the nqcc's. |
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Table 1. Br nqcc's in
axial Bromocyclopentane
(MHz). Calculation was made on (1) PBE1PBE/6-31G(3d,3p) and (2)
M06-2X/6-31G(3d,3p) ropt structures.
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Calc (1)
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Calc (2)
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Expt [1]
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Xaa (79Br) |
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282.85 |
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276.83 |
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274.2(13) |
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Xbb |
- |
264.80 |
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264.59 |
- |
264.7(11) |
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Xcc |
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- 18.06 |
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- 12.24 |
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- 9.5(13) |
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|Xac| |
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363.42 |
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366 83 |
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RMS
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7.0 (3.8 %) |
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2.2 (1.2 %) |
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RSD |
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1.58 (0.39 %) |
1.58 (0.39 %) |
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Xxx |
- |
260.93 |
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261.98 |
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Xyy |
- |
264.80 |
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264.59 |
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Xzz |
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525.73 |
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526.57 |
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ETA |
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0.00735 |
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0.00495 |
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Øz,a |
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33.76 |
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34.25 |
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ØCBr,a |
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34.18 |
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34.51 |
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Øz,CBr |
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0.42 |
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0.27 |
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Xaa (81Br) |
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237.13 |
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232.12 |
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239.2(32) |
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Xbb |
- |
221.23 |
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221.06 |
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222.4(20) |
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Xcc |
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- 15.90 |
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- 11.06 |
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- 16.8(27) |
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|Xac| |
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303.28 |
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306.15 |
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RMS |
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1.5 (0.92 %) |
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5.3 (3.3 %) |
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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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Table 2. Br nqcc's in
equatorial Bromocyclopentane
(MHz). Calculation was made on (1) PBE1PBE/6-31G(3d,3p) and (2)
M06-2X/6-31G(3d,3p) ropt structures.
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Calc (1)
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Calc (2)
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Expt [1]
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Xaa (79Br) |
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481.77 |
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482.71 |
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444.7(23) |
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Xbb |
- |
266.22 |
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266.62 |
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279.1(43) |
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Xcc |
- |
215.55 |
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216.10 |
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165.6(47) |
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|Xac| |
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192.61 |
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191.57 |
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RMS
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36.7 (12.4 %) |
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37.2(12.5 %) |
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RSD |
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1.58 (0.39 %) |
1.58 (0.39 %) |
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Xxx |
- |
265.22 |
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265.17 |
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Xyy |
- |
266.22 |
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266.62 |
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Xzz |
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531.44 |
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531.79 |
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ETA |
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0.00187 |
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0.00272 |
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Øz,a |
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14.56 |
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14.38 |
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Øa,CBr |
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13.54 |
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13.39 |
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Øz,CBr |
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0.92 |
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0.98 |
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Xaa (81Br) |
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402.55 |
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403.34 |
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391.5(26) |
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Xbb |
- |
222.41 |
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222.75 |
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228.8(67) |
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Xcc |
- |
180.14 |
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180.59 |
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162.7(77) |
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|Xac| |
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160.88 |
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159.97 |
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RMS |
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12.5 (4.8 %) |
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13.0 (5.0 %) |
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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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| Table
3. Bromocyclopentane, Rotational Constants, 79Br
species (MHz). ropt(1) = PBE1PBE/6-31G(3d,3p), ropt(2)
= M06-2X/6-31G(3d,3p) ropt structures. |
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axial
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ropt(1) |
ropt(2) |
Expt. [1]
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A
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4424.9 |
4383.9 |
4395.5467(69) |
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B
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1535.3 |
1549.9 |
1511.1364(7) |
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C
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1450.2 |
1467.4 |
1428.7677(7) |
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equatorial |
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A
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6453.3 |
6452.5 |
6460.6(15) |
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B
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1190.7 |
1189.0 |
1175.9883(76) |
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C
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1052.1 |
1051.0 |
1039.9382(75) |
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[1]
J.R.Durig, W.Zhao, and X.Zhu, J.Mol.Struct. 521,25(2000).
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Bromocyclopropane |
Bromocyclobutane |
Bromocyclohexane |
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Table of Contents |
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Molecules/Bromine |
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Brcycpent.html |
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Last
Modified 23 Sept 2013 |
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