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CH3CH2CH2-C(=O)Cl
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in
syn-anti Butyryl Chloride |
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Chlorine nqcc's in the syn-anti
conformer of butyryl chloride have been determined by Powoski, et al.
[1].
Calculation was made here of the nqcc tensors on molecular
structure given by MP2/6-311+G(d,p) and MP2/6-311+G(2d,p) optimization
with approximate
equilibrium (~ re) bond lengths derived as described here.
Calculated and experimental nqcc's are compared in Tables 1 and
2.
Structure parameters are given in Table 3, rotational constants
in Table 4. |
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In Tables 1 and 2, 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 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 nqcc's, which may be
taken as an estimate of the uncertainty in the calculated nqcc's
(notwithstanding uncertainties in the optimized structures). |
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Table 1. 35Cl
nqcc's in syn-anti CH3CH2CH2-C(=O)Cl
(MHz). Calculation was made on (1) MP2/6-311+G(d,p) and (2)
MP2/6-311+G(2d,p) optimized structures each with ~ re bond
lengths. |
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Calc (1) |
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Calc (2) |
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Expt. [1] |
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Xaa |
- |
32.21 |
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31.83 |
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32.1496(51) |
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Xbb |
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10.23 |
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9.94 |
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9.6649(76) |
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Xcc |
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21.98 |
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21.89 |
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22.4847(56) |
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|Xab| |
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44.32 |
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44.35 |
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43.18(23) |
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RMS |
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0.44 (2.0 %) |
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0.42 (2.0 %) |
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RSD |
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0.49 (1.1 %) |
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0.49 (1.1 %) |
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Xxx |
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38.15 |
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38.08 |
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36.73(21) |
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Xyy |
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21.98 |
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21.89 |
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22.485(6) |
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Xzz |
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60.12 |
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59.96 |
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59.22(21) |
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ETA |
- |
0.269 |
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0.270 |
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0.2406(36) |
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Øz,a |
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32.21 |
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32.39 |
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32.082(60) |
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Øa,CCl |
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32.60 |
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32.82 |
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Øz,CCl |
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0.39 |
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0.43 |
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Table 2. 37Cl
nqcc's in syn-anti CH3CH2CH2-C(=O)Cl
(MHz). Calculation was made on (1) MP2/6-311+G(d,p) and (2)
MP2/6-311+G(2d,p) optimized structures each with ~ re bond
lengths. |
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Calc (1) |
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Calc (2) |
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Expt. [1] |
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Xaa |
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25.87 |
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25.58 |
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25.802(18) |
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Xbb |
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8.56 |
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8.33 |
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8.210(28) |
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Xcc |
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17.32 |
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17.25 |
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17.682(21) |
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|Xab| |
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34.69 |
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34.71 |
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34.44(99) |
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RMS |
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0.33 (1.9 %) |
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0.31 (1.8 %) |
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RSD |
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0.44 (1.1 %) |
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0.44 (1.1 %) |
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Xxx |
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30.06 |
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30.01 |
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Xyy |
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17.32 |
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17.25 |
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Xzz |
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47.38 |
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47.26 |
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ETA |
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0.269 |
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0.270 |
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Øz,a |
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31.80 |
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31.98 |
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Øa,CCl |
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32.19 |
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32.41 |
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Øz,CCl |
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0.39 |
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0.43 |
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| Table 2. syn-anti Butyryl
Chloride. Heavy atom structure parameters, (1)
MP2/6-311+G(d,p) and (2) MP2/6-311+G(2d,p) optimized structures each
with ~ re bond lengths. (Å and degrees).
Complete structures are given
here in Z-matrix format. |
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~ re(1) |
~ re(2) |
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| C(1)C(11) |
1.4997 |
1.4997 |
| C(11)=O |
1.1845 |
1.1845 |
| C(11)Cl |
1.8038 |
1.8038 |
| C(1)C(11)=O |
127.45 |
127.90 |
| C(1)C(11)Cl |
111.95 |
111.75 |
| C(1)C(2) |
1.5176 |
1.5176 |
| C(2)C(3) |
1.5204 |
1.5204 |
| C(11)C(1)C(2) |
112.82 |
112.83 |
| C(1)C(2)C(3) |
111.36 |
111.17 |
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| Table 3. syn-anti Butyryl
Chloride. Rotational constants (MHz). 35Cl
species. |
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~ re(1) |
~ re(2) |
Expt. [1] |
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A |
6859.32 |
6833.93 |
6835.9011(15) |
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B |
1321.49 |
1323.54 |
1313.97956(23) |
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C |
1131.08 |
1131.83 |
1125.24433(19) |
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[1] R.A.Powoski, G.S.Grubbs II, and
S.A.Cooke, J.Mol.Struct. 963,106(2010). |
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HC(=O)Cl |
FC(=O)Cl |
CH3C(=O)Cl |
CH2BrC(=O)Cl |
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CH2FC(=O)Cl |
HCCC(=O)Cl |
syn-trans-CH2=CH-C(=O)Cl |
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(CH3)3C-C(=O)Cl |
syn-gauche
CH3CH2CH2-C(=O)Cl |
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Table of Contents |
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Molecules/Chlorine |
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tCH3CH2CH2COCl.html |
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Last
Modified 20 Oct 2009 |
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