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CH3CH2C(=O)Cl
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in
Propionyl Chloride |
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Microwave spectroscopic studies of
propionyl chloride were undertaken by Karlsson [1] and by Mata and
Alonso [2], and revisited by Grubbs II, et al [3]. |
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Calculation of the Cl nqcc
tensor in propionyl chloride was made here on an ~re
structure given by MP2/aug-cc-pVTZ
optimization with empirically corrected equilibrium
CCl, C-C, and C=O bond lengths. These are compared with the
experimental nqcc's [3] 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; subscripts
x,y,z to the principal axes of the nqcc tensor. The nqcc y-axis
is chosen coincident with the c-axis. Ø (degrees) is the
angle between its subscripted parameters. ETA = (Xxx -
Xyy)/Xzz. |
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RMS is the root measn square
difference between calculated and experimental diagonal nqcc's (percent
of the average of the absolute experimental nqcc's). RSD is the
residual standard deviation of the calibration of the computional model
for calculation of the nqcc's. |
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Table 1. 35Cl
nqcc's
in CH3CH2C(=O)Cl (MHz).
Calculation was made on the ~re molecular structure. |
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Calc. |
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Expt. [3] |
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35Cl |
Xaa |
- |
48.92 |
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49.0673(37) |
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Xbb |
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27.11 |
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26.4986(55) |
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Xcc |
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21.81 |
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22.5687(40) |
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|Xab| |
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30.94 |
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29.94(57) |
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RMS |
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0.57 (1.7 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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38.11 |
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36.92(35) |
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Xyy |
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21.81 |
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22.569(4) |
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Xzz |
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59.92 |
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59.49(35) |
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ETA |
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0.272 |
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0.2413(61) |
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Øz,a |
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19.57 |
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19.20 |
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Øa,CCl |
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19.94 |
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Øz,CCl |
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0.37 |
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Table 2. 37Cl
nqcc's
in CH3CH2C(=O)Cl (MHz).
Calculation was made on the ~re molecular structure. |
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Calc. |
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Expt. [3] |
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37Cl |
Xaa |
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38.85 |
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38.9625(51) |
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Xbb |
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21.66 |
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21.1725(80) |
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Xcc |
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17.19 |
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17.7900(61) |
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|Xab| |
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24.02 |
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23.75(40) |
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RMS |
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0.45 (1.7 %) |
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RSD |
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0.44 (1.1 %) |
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Xxx |
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30.04 |
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Xyy |
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17.19 |
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Xzz |
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47.22 |
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ETA |
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0.272 |
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Øz,a |
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19.23 |
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Øa,CCl |
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19.60 |
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Øz,CCl |
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0.37 |
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| Table 3.
Propionyl Chloride. Heavy atom structure parameters, ~re
(Å and degrees). The complete structure is given here in Z-matrix format. |
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| Cs |
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~re |
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| ClC(8) |
1.7984 |
| C(8)O |
1.1832 |
| C(8)C(1) |
1.4990 |
| C(1)C(2) |
1.5171 |
| C(1)C(8)Cl |
111.53 |
| C(1)C(8)O |
127.94 |
| C(2)C(1)C(8) |
112.19 |
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| Table 4.
Propionyl Chloride. Rotational Constants (MHz). 35Cl species. |
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~re |
Expt. [3] |
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A |
8877.8 |
8854.7845(14) |
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B |
2398.0 |
2377.94361(37) |
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C |
1932.6 |
1918.68343(24) |
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[1] H.Karlsson,
J.Mol.Struct. 33,227(1976). |
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[2] F.Mata and J.L.Alonso,
J.Mol.Struct. 56,199(1979). |
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[3] G.S.Grubbs II, R.A.Powoski,
D.Jojola, and S.A.Cooke, J.Phys.Chem. A 114,8009(2010). |
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HC(=O)Cl |
CH3C(=O)Cl |
(CH3)3C-C(=O)Cl |
FC(=O)Cl |
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ClCH2C(=O)F |
BrCH2C(=O)Cl |
FCH2C(=O)Cl |
HCCC(=O)Cl |
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ClCH2C(=O)Cl |
s-t-CH2=CHC(=O)Cl |
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Table of Contents |
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Molecules/Chlorine |
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CH3CH2COCl.html |
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Last
Modified 3 Aug 2010 |
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