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(CH3)2-CH-CH2Cl
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in gauche-Isobutyl Chloride
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Calculation of the chlorine nqcc's in gauche-isobutyl chloride
was made on approximate equilibrium structures given by MP2 optimization in conjunction with Pople-type bases with empirical correction for the CH, C-C, and CCl bond lengths (~ re); and on a structure given by MP2/aug-cc-pVTZ optimization with and without empirical correction of bond lengths.
These are compared with the experimental nqcc's of Niide and Ohkoshi
[1] in Tables 1 - 4. Structure parameters are given in
Table 5, rotational constants in Table 6. |
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In Tables 1 - 4,
subscripts a,b,c refer to the
principal axes of the inertia tensor; x,y,z to the principal axes
of the nqcc tensor. Øz,CCl (degrees) is the angle between the principal z-axis of the nqcc tensor and the CCl bond axis. ETA = (Xxx - Xyy)/Xzz. |
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RMS is the root mean
square difference between calculated and experimental diagonal nqcc's.
RSD is the calibration residual standard deviation of
the B1LYP/TZV(3df,3p) model for calculation of the chlorine nqcc's. |
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Table 1.
35Cl nqcc's in gauche-isobutyl chloride (MHz). Calculation was made on the ~ re structure, with interatomic angles given by (1) MP2/6-311+G(d,p) and (2) MP2/6-311+G(2d,p) optimizations. |
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Calc/~ re(1)
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Calc/~ re(2) |
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Expt. [1] |
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Xaa |
- |
47.60 |
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48.21 |
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51.6(54) |
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Xbb |
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19.12 |
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18.94 |
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16.9(28) |
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Xcc |
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28.48 |
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29.27 |
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34.7(60) |
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Xab |
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36.87 |
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37.04 |
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Xac |
-
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23.67 |
-
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22.13 |
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Xbc |
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11.20 |
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10.59 |
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RMS |
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4.4 (13.0 %) |
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3.9 (11.3 %) |
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RSD |
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0.49 (1.1 %) |
0.49 (1.1 %) |
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Xxx |
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34.81 |
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34.63 |
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Xyy |
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36.05 |
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36.02 |
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Xzz |
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70.86 |
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70.65 |
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ETA |
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0.0176 |
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0.0197 |
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Øz,CCl |
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0.78 |
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0.59 |
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Table 2.
35Cl nqcc's in gauche-isobutyl chloride (MHz). Calculation was made on the MP2/aug-cc-pVTZ ropt and ~ re structures.
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Calc/ropt
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Calc/~ re |
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Expt. [1] |
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Xaa |
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47.93 |
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47.81 |
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51.6(54) |
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Xbb |
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18.73 |
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18.68 |
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16.9(28) |
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Xcc |
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29.20 |
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29.13 |
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34.7(60) |
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Xab |
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37.33 |
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37.29 |
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Xac |
-
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22.29 |
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22.27 |
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Xbc |
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10.74 |
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10.74 |
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RMS |
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4.0 (11.5 %) |
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4.0 (11.7 %) |
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RSD |
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0.49 (1.1 %) |
0.49 (1.1 %) |
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Xxx |
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34.70 |
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34.65 |
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Xyy |
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36.06 |
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36.00 |
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Xzz |
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70.76 |
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70.65 |
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ETA |
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0.0191 |
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0.0191 |
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Øz,CCl |
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0.65 |
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0.66 |
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Table 3.
37Cl nqcc's in gauche-isobutyl chloride (MHz). Calculation was made on the ~ re structure, with interatomic angles given by (1) MP2/6-311+G(d,p) and (2) MP2/6-311+G(2d,p) optimizations. |
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Calc/~ re(1)
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Calc/~ re(2) |
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Expt. [1] |
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Xaa |
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37.55 |
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38.03 |
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39.3(99) |
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Xbb |
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15.07 |
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14.93 |
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14.3(77) |
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Xcc |
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22.48 |
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23.10 |
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25.0(125) |
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Xab |
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29.07 |
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29.20 |
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Xac |
-
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18.59 |
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17.37 |
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Xbc |
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8.80 |
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8.32 |
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RMS |
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1.8 (7.0 %) |
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1.4 (5.2 %) |
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RSD |
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0.49 (1.1 %) |
0.49 (1.1 %) |
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Table 4.
37Cl nqcc's in gauche-isobutyl chloride (MHz). Calculation was made on the MP2/aug-cc-pVTZ ropt and ~ re structures. |
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Calc/ropt
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Calc/~ re |
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Expt. [1] |
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Xaa |
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37.80 |
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37.71 |
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39.3(99) |
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Xbb |
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14.76 |
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14.72 |
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14.3(77) |
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Xcc |
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23.04 |
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23.00 |
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25.0(125) |
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Xab |
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29.44 |
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29.40 |
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Xac |
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17.50 |
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17.49 |
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Xbc |
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8.43 |
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8.43 |
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RMS |
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1.4 (5.5 %) |
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1.5 (5.7 %) |
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RSD |
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0.49 (1.1 %) |
0.49 (1.1 %) |
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| Table 5(a). gauche-isobutyl chloride. Heavy atom structure parameters, ~ re(1) and ~ re(2) (Å
and degrees). Complete structures are given here in Z-matrix format. |
| ~ re(1) is ~ re bond lengths with MP2/6-311+G(d,p) interatomic angles, ~ re(2) is ~ re bond lengths with MP2/6-311+G(2d,p) angles. |
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~ re(1) |
~ re(2) |
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| C(2)C(3) |
1.5153 |
1.5153 |
| C(2)C(4) |
1.5232 |
1.5232 |
| C(2)C(5) |
1.5197 |
1.5197 |
| C(3)Cl |
1.7870 |
1.7870 |
| C(4)C(2)C(3) |
108.67 |
108.19 |
| C(5)C(2)C(3) |
111.84 |
111.98 |
| C(4)C(2)C(5) |
110.80 |
110.88 |
| C(2)C(3)Cl |
112.26 |
112.70 |
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| Table 5(b). gauche-isobutyl chloride. Heavy atom structure parameters, MP2/aug-cc-pVTZ ropt and ~ re(2) (Å
and degrees). Complete structures are given here in Z-matrix format. |
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ropt |
~ re |
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| C(2)C(3) |
1.5176 |
1.5157 |
| C(2)C(4) |
1.5268 |
1.5245 |
| C(2)C(5) |
1.5224 |
1.5202 |
| C(3)Cl |
1.7916 |
1.7883 |
| C(4)C(2)C(3) |
108.30 |
108.30 |
| C(5)C(2)C(3) |
111.67 |
111.67 |
| C(4)C(2)C(5) |
110.85 |
110.85 |
| C(2)C(3)Cl |
112.28 |
112.28 |
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| Table 6. Rotational Constants (MHz). 35Cl Species. |
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MP2/Pople
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MP2/aug-cc-pVTZ
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~ re(1) |
~ re(2) |
ropt |
~ re |
Expt. [1] |
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A |
7628 |
7626 |
7622
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7640
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7498.57(62) |
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B |
2166 |
2166 |
2165
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2172
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2146.321(16) |
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C |
1814 |
1812 |
1811
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1817
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1793.715(9) |
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[1] Y.Niide and I.Ohkoshi, J.Mol.Spectrosc. 146,334(1991).
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t-Butyl Chloride |
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Table of Contents |
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Molecules/Chlorine |
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gCH32CHCH2Cl.html |
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Last
Modified 20 Feb 2014 |
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