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t-3-Cl-C6H4OH
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Chlorine, Hydroxyl Deuterium, and Oxygen
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Nuclear
Quadrupole Coupling Constants |
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in trans-3-Chlorophenol |
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Calculation of the chlorine, hydroxyl
deuterium, and oxygen nqcc's in t-3-chlorophenol was made on the molecular structure given by B3P86/6-31G(3d,3p)
optimization. These nqcc's are given in Tables 1 - 3. Structure parameters and atomic coordinates are given
in Tables 4 and 5, respectively. Rotational constants are given in
Table 6. (Chlorine is 'trans'
with respect to the hydroxyl hydrogen.) |
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In Tables 1 - 3, subscripts a,b,c
refer to the principal axes of the inertia tensor; x,y,z to the
principal axes of the nqcc tensor. The nqcc y-axis is chosen
coincident with the inertia c-axis, these are perpendicular to the
molecular plane. Ø (degrees) is the angle between its
subscripted parameters. ETA = (Xxx - Xyy)/Xzz. RSD is
the calibration residual standard deviation of the model for
calculation of the nqcc's.
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Table 1. Chlorine
nqcc's in t-3-Cl-C6H4OH (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
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Calc. |
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Expt. |
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35Cl |
Xaa |
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61.82 |
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Xbb |
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29.17 |
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Xcc |
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32.65 |
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|Xab| |
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32.07 |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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39.34 |
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Xyy |
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32.65 |
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Xzz |
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71.99 |
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ETA |
- |
0.093 |
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Øz,a |
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17.59 |
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Øa,CCl |
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17.65 |
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Øz,CCl |
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0.06 |
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Table 2. Deuterium
nqcc's in t-3-Cl-C6H4OD (kHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
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Calc. |
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Expt. |
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2H |
Xaa |
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211.0 |
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Xbb |
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- 48.4 |
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Xcc |
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162.6 |
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|Xab| |
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158.4 |
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RSD |
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1.1 (0.86 %) |
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Xxx |
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123.4 |
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Xyy |
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162.6 |
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Xzz |
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286.0 |
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ETA |
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0.137 |
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Øz,a |
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25.34 |
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Øa,OD |
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26.10 |
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Øz,OD |
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0.76 |
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In solid 3-chlorophenol,
Batchelder et al. [1] observed in the pure nuclear quadrupole spectra
(NQR) two pairs of deuteron lines corresponding to two
crystallographically inequivalent sites. At 77 K, Xzz and ETA for
these are 219.39 kHz and 0.161, and 208.31 kHz and 0.152.
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Table 3. Oxygen
nqcc's in t-3-Cl-C6H4OH (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
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Calc = B1LYP/6-311++G(3df,3p) |
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Calc. |
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Expt. |
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17O |
Xaa |
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9.183 |
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Xbb |
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0.369 |
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Xcc |
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8.815 |
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|Xab| |
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2.127 |
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RSD |
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0.041 (1.4 %) |
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Xxx |
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0.821 |
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Xyy |
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8.815 |
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Xzz |
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9.636 |
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ETA |
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0.830 |
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Øz,a |
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12.00 |
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Øa,OH |
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26.15 |
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Øz,OH |
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38.15 |
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| Table 4. Molecular structure parameters, ropt (Å
and degrees). |
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C(3)Cl |
1.7358 |
C(2)C(3)Cl |
118.78 |
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C(1)C(2) |
1.3934 |
C(1)C(2)C(3) |
118.71 |
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C(2)C(3) |
1.3863 |
C(2)C(3)C(4) |
122.01 |
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C(3)C(4) |
1.3903 |
C(3)C(4)C(5) |
118.26 |
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C(4)C(5) |
1.3885 |
C(4)C(5)C(6) |
121.09 |
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C(5)C(6) |
1.3889 |
C(5)C(6)C(1) |
119.54 |
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C(6)C(1) |
1.3934 |
C(6)C(1)C(2) |
120.38 |
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C(1)O(1) |
1.3574 |
C(2)C(1)O(1) |
116.89 |
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O(1)H |
0.9621 |
C(1)O(1)H |
109.19 |
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C(2)H(2) |
1.0824 |
C(1)C(2)H(2) |
119.99 |
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C(4)H(4) |
1.0823 |
C(3)C(4)H(4) |
120.24 |
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C(5)H(5) |
1.0846 |
C(4)C(5)H(5) |
119.49 |
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C(6)H(6) |
1.0863 |
C(5)C(6)H(6) |
120.41 |
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| Table 5. Atomic coordinates, ropt. Normal species. |
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a (Å) |
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b (Å) |
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Cl |
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2.427776 |
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0.449696 |
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C(1) |
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1.558082 |
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0.454864 |
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C(2) |
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0.230731 |
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0.878825 |
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C(3) |
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0.773668 |
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0.076703 |
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C(4) |
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0.494961 |
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1.438817 |
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C(5) |
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0.834978 |
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1.837827 |
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C(6) |
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1.863735 |
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0.904648 |
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O(1) |
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2.511287 |
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1.421243 |
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H |
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3.380301 |
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1.008312 |
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H(2) |
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0.000516 |
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1.936423 |
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H(4) |
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1.301695 |
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2.160356 |
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H(5) |
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1.075027 |
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2.895516 |
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H(6) |
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2.900440 |
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1.229080 |
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| Table 6. Rotational Constants
(MHz). Normal species. |
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Calc ropt |
Expt |
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A |
3464.4 |
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B |
1203.9 |
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C |
893.4 |
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[1] L.S.Batchelder, J.Clymer, and J.L.Rangle, J.Chem.Phys.
74,4791(1981). |
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Chlorobenzene
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Phenol
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1,2-Dichlorobenzene |
1,2-Chlorofluorobenzene |
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1,3-Dichlorobenzene |
1,3-Chlorofluorobenzene |
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1,4-Dichlorobenzene |
1,4-Chlorofluorobenzene |
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Bromobenzene |
4-Chlorophenol |
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Fluorobenzene |
trans-2-Chlorophenol |
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Benzonitrile |
cis-3-Chlorophenol |
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Table of Contents
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Molecules/Chlorine |
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Molecules/Deuterium |
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Molecules/Oxygen |
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t3Clphenol.html |
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Last
Modified 8 Nov 2004 |
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