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C6H5Br |
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Bromine |
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Nuclear
Quadrupole Coupling Constants |
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in Bromobenzene |
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Bromine nqcc's in bromobenzene were first reported in 1971 by Caminati
and Mirri [1], revisited in 2003 by Peebles and Peebles [2], and in 2007 by Dorosh et al. [3]. |
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Bromine nqcc's were calculated here on B3P86/6-31G(3d,3p)
and PBE1PBE/6-31G(3d,3p) optimized molecular structures. These are compared in Tables 1 and 2 with
the experimental values [3]. Structure parameters
are compared in Table 3. |
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In Tables 1 and 2, RMS is the root measn square
difference between calculated and experimental diagonal nqcc. RSD
is the residual standard deviation of the calibration of the
computional model for calculation of the nqcc's. ETA = (Xbb - Xcc)/Xaa = (Xxx
- Xyy)/Xzz. |
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Table 1. Bromine nqcc's in C6H5Br (MHz). Calculation was made on the B3P86/6-31G(3d,3p) structure. |
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Calc. |
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Expt. [3] |
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79Br |
Xaa |
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559.12 |
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556.6783(17)
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Xbb |
- |
294.66 |
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292.8470(43)
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Xcc |
- |
264.46 |
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263.8314(43) |
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ETA |
- |
0.0550 |
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0.052123(11) |
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RMS |
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1.79 (0.48 %) |
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RSD |
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1.58 (0.39 %) |
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81Br |
Xaa |
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467.13 |
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465.0471(19) |
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Xbb |
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246.18 |
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244.6428(39) |
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Xcc |
- |
220.95 |
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220.4044(39) |
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ETA |
- |
0.0550 |
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0.052120(12) |
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RMS |
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1.53 (0.49 %) |
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RSD |
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1.38 (0.40 %) |
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Table 2. Bromine nqcc's in C6H5Br (MHz). Calculation was made on the PBE1PBE/6-31G(3d,3p) structure. |
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Calc. |
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Expt. [3] |
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79Br |
Xaa |
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557.89 |
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556.6783(17) |
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Xbb |
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294.29 |
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292.8470(43) |
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Xcc |
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263.61 |
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263.8314(43) |
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ETA |
- |
0.0550 |
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0.052123(11) |
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RMS |
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1.10 (0.30 %) |
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RSD |
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1.58 (0.39 %) |
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81Br |
Xaa |
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466.10 |
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465.0471(19) |
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Xbb |
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245.87 |
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244.6428(39) |
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Xcc |
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220.24 |
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220.4044(39) |
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ETA |
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0.0550 |
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0.052120(12) |
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RMS |
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0.94 (0.30 %) |
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RSD |
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1.38 (0.40 %) |
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| Table 3. Molecular structure parameters (Å and degrees). Method/6-31G(3d,3p). |
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B3P86 |
PBE1PBE |
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C(1)Br |
1.8797 |
1.8765 |
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C(1)C(2) |
1.3884 |
1.3884 |
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C(2)C(3) |
1.3898 |
1.3897 |
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C(3)C(4) |
1.3898 |
1.3896 |
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C(2)H(2) |
1.0827 |
1.0835 |
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C(3)H(3) |
1.0847 |
1.0856 |
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C(4)H(4) |
1.0843 |
1.0852 |
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C(6)C(1)C(2) |
120.94 |
120.94 |
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C(1)C(2)C(3) |
119.26 |
119.26 |
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C(2)C(3)C(4) |
120.44 |
120.43 |
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C(3)C(4)C(5) |
119.66 |
119.68 |
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C(1)C(2)H(2) |
120.03 |
119.99 |
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C(2)C(3)H(3) |
119.41 |
119.44 |
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For comparison, the
B3P86/6-31G(3d,3p) optimized molecular structure of benzene is CC =
1.3909 Å and CH = 1.0851 Å; the PBE1PBE/6-31G(3d,3p)
optimized parameters are respectively 1.3908Å and 1.0860 Å. |
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[1] W.Caminati and A.M.Mirri, Chem.Phys.Lett. 12,127(1971). |
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[2] S.A.Peebles and R.A.Peebles, J.Mol.Struct. 657,107(2003). |
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[3] O.Dorosh, E.Białkowska-Jaworska, Z.Kisiel, and L.Pszczółkowski, J.Mol.Spectrosc. 246,228(2007). |
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K.C.Etchison, C.T.Dewberry, K.E.Kerr, D.W.Shoup, and S.A.Cooke, J.Mol.Spectrosc. 242,39(2007). Xaa (79Br) = 556.689(10) MHz and Xbb - Xcc = - 29.031(104) MHz. |
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C6H5Cl |
C6H5CN |
C6H5BF2 |
C6H5F |
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Table of Contents |
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Molecules/Bromine |
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C6H5Br.html |
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Last
Modified 3 Oct 2007 |
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