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CH2CH2CHCl |
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in Cyclopropyl Chloride |
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Calculation of the chlorine nqcc's in cyclopropyl chloride was made on the substitution structure of Schwendeman et al. [1], and on an ropt
structure obtained by MP2/6-311+G(2d,p) optimization. These are
compared with the experimental nqcc's in Tables 1 and 2.
Structure parameters are compared in Table 3. |
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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. The nqcc y-axis is chosen coincident with the
inertia b-axis, these are perpendicular to the molecular symmetry plane.
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 for the B1LYP/TZV(3df,2p) model
for calculation of the chlorine nqcc's. |
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Table 1. Chlorine
nqcc's in cyclic CH2CH2CHCl (MHz). Calculation was made on the substitution molecular structure of Schwendeman et al. [1]. |
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Calc. |
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Expt. [1] |
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35Cl |
Xaa |
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56.78 |
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56.64(40) |
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Xbb |
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37.84 |
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36.72(22) |
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Xcc |
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18.94 |
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19.92(22) |
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|Xac| |
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39.23 |
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RMS |
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0.86 (2.3 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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35.60 |
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36.45 * |
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Xyy |
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37.84 |
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36.72 |
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Xzz |
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73.44 |
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73.17 |
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ETA |
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0.030 |
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0.004 |
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Øz,a |
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23.01 |
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22.85 |
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Øa,CCl |
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21.8 |
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21.8 |
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Øz,CCl |
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1.2 |
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1.0 |
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37Cl |
Xaa |
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44.86 |
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Xbb |
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29.82 |
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Xcc |
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15.04 |
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|Xac| |
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30.81 |
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* Calculated here from the experimental diagonal
nqcc's and the calculated off-diagonal nqcc. |
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Table 2. Chlorine
nqcc's in cyclic CH2CH2CHCl (MHz). Calculation was made on the MP2/6-311+G(2d,p) ropt molecular structure (see below). |
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Calc. |
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Expt. [1] |
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35Cl |
Xaa |
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57.82 |
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56.64(40) |
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Xbb |
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37.28 |
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36.72(22) |
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Xcc |
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20.54 |
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19.92(22) |
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|Xac| |
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37.40 |
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RMS |
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0.84 (2.2 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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35.53 |
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35.16 * |
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Xyy |
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37.28 |
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36.72 |
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Xzz |
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72.81 |
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71.88 |
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ETA |
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0.024 |
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0.022 |
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Øz,a |
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21.84 |
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22.17 |
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Øa,CCl |
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21.28 |
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21.28 |
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Øz,CCl |
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0.55 |
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0.89 |
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* Calculated here from the experimental diagonal
nqcc's and the calculated off-diagonal nqcc. |
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| Table 3. Molecular structure parameters (Å and degrees). Z-Matrix |
| ropt = MP2/6-311+G(2d,p) optimization with corrected CCl bond length [2]. |
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rs
[1] |
ropt |
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C(1)Cl |
1.740(3) |
1.7508 |
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C(1)C(2,3) |
1.513(4) |
1.4956 |
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C(2)C(3) |
1.515(1) |
1.5178 |
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CHs |
1.079(1) |
1.0808 |
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CHc |
1.086(4) |
1.0818 |
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CHt |
1.082(3) |
1.0825 |
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CCCl |
118.7(3) |
119.06 |
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ClCH |
115.8(2) |
111.60 |
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CCHs |
116.1(3) |
118.88 |
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C(1)C(3)Hc |
115.5(2) |
116.92 |
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C(2)C(3)Hc |
116.9(4) |
116.87 |
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C(1)C(3)Ht |
117.8(4) |
117.46 |
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C(2)C(3)Ht |
118.7(3) |
118.75 |
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HCH |
116.2(3) |
115.72 |
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[1] R.H.Schwendeman, G.D.Jacobs, and T.M.Krigas, J.Chem.Phys. 40,1022(1964). |
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[2] I.Merke, L.Poteau, G.Wlodarczak, A.Bouddou, and J.Demaison, J.Mol.Spectrosc. 177,232(1996). |
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CH2CH2CCl2 |
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Table of Contents |
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Molecules/Chlorine |
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CH2CH2CHCl.html |
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Last
Modified 1 June 2006 |
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