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1,3-Chlorofluorobenzene
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in 1,3-Chlorofluorobenzene |
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35Cl nqcc's in 1,3-chlorofluorobenzene were first determined
in 1973 by Kirty and Srivastava [1], and redetermined in 1994 by molecular
beam Fourier Transform microwave spectroscopy by Onda et al. [2]. |
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Chlorine nqcc's were calculated here on a molecular structure
determined by B3P86/6-31G(3d,3p) optimization. These calculated nqcc's
are compared with the experimental values in Table 1. Structure parameters
and atomic coordinates are given in Tables 2 and 3, respectively. |
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In Table 1, RMS is the root mean square difference between calculated
and experimental nqcc's (percentage of the average of the magnitudes of
the experimental nqcc's). RSD is the calibration residual standard
deviation for the B1LYP/TZV(3df,2p) model for calculation of the nqcc's. |
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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. |
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Table 1. Chlorine
nqcc's in 1,3-Chlorofluorobenzene (MHz). Calculation was made on the B3P86/6-31G(3d,3p) ropt structure. |
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Calc. |
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Expt. [2] |
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35Cl |
Xaa |
- |
61.72 |
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61.3242(33) |
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Xbb |
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28.80 |
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28.1056(27) |
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Xcc |
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32.92 |
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33.2186(60) |
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|Xab| |
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33.19 |
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32.989(25) |
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RMS |
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0.49 (1.2 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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39.66 |
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38.9588(26) |
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Xyy |
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32.92 |
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33.2186(60) |
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Xzz |
- |
72.58 |
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72.1774(34) |
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ETA |
- |
0.093 |
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0.080 |
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Øz,a |
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18.13 |
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18.21 |
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Øa,CCl |
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18.19 |
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18.19 * |
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Øz,CCl |
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0.06 |
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0.02 * |
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37Cl |
Xaa |
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49.04 |
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Xbb |
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23.09 |
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Xcc |
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25.94 |
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|Xab|
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25.61 |
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RSD |
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0.44 (1.1 %) |
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* Calculated here. |
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The nqcc z-axis makes an angle of 0.06o with the CCl
bond axis. In 1,3-dichlorobenzene, this angle is 0.09o.
On the other hand, in 1,2-chlorofluorobenzene and 1,2-dichlorobenzene, this
angle is1.07o and 1.21o respectively. (Calculated
nqcc's, ropt structures.) |
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| Table 2. Molecular structure parameters, ropt (Å and degrees). |
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C(1)Cl(1) |
1.7333 |
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C(3)F(3) |
1.3406 |
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C(1)C(2) |
1.3891 |
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C(2)C(3) |
1.3849 |
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C(3)C(4) |
1.3845 |
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C(4)C(5) |
1.3898 |
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C(5)C(6) |
1.3899 |
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C(6)C(1) |
1.3899 |
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C(2)H(2) |
1.0822 |
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C(4)H(4) |
1.0830 |
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C(5)H(5) |
1.0844 |
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C(6)H(6) |
1.0825 |
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C(6)C(1)C(2) |
121.60 |
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C(1)C(2)C(3) |
117.61 |
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C(2)C(3)C(4) |
122.74 |
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C(3)C(4)C(5) |
118.11 |
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C(4)C(5)C(6) |
121.07 |
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C(5)C(6)C(1) |
118.87 |
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C(2)C(1)Cl(1) |
118.93 |
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C(2)C(3)F(3) |
118.29 |
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C(1)C(2)H(2) |
121.86 |
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C(1)C(6)H(6) |
119.98 |
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C(3)C(4)H(4) |
119.79 |
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C(6)C(5)H(5) |
119.41 |
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For comparison with the optimized structure, the B3P86/6-31G(3d,3p)
optimized structure of benzene is CC = 1.3909 Å and CH = 1.0851
Å. |
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| Table 3. Atomic Coordinates, ropt |
| (More figures are shown than are significant.) |
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a (Å) |
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b (Å) |
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Cl(1) |
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2.457696 |
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0.463654 |
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F(3) |
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2.505518 |
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1.305481 |
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C(1) |
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0.811078 |
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0.077491 |
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C(2) |
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0.206880 |
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0.867722 |
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C(3) |
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1.512245 |
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0.405094 |
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C(4) |
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1.829071 |
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0.942678 |
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C(5) |
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0.785556 |
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1.860684 |
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C(6) |
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0.539302 |
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1.440560 |
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H(2) |
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0.000034 |
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1.929936 |
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H(4) |
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1.251441 |
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2.867094 |
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H(5) |
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1.007757 |
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2.922064 |
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H(6) |
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2.154358 |
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1.353138 |
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[1] K.K.Kirty and S.L.Srivastava, Indian J. Pure Appl. Phys. 11,293(1973). |
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[2] M.Onda, T.Odaka, H.Miyazaki, M.Mori,
I.Yamaguchi, and Y.Niide, J.Mol.Spectrosc. 165,426(1994). |
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Chlorobenzene |
1,2-Dichlorobenzene |
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1,3-Dichlorobenzene |
1,2-Chlorofluorobenzene |
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1,4-Dichlorobenzene |
1,4-Chlorofluorobenzene |
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cis-2-Chlorophenol |
trans-2-Chlorophenol |
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Table of Contents |
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Molecules/Chlorine |
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13CFB.html |
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Last
Modified 4 June 2003 |
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