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CF3CF2C(=O)Cl
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in
Perfluoropropionyl Chloride |
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Calculation of the Cl nqcc
tensor in propionyl chloride was made here on structures given by
(1) MP2/6-311+G(3df,3pd)
optimization with approximate re bond lengths and
(2) MP2/aug-cc-pVTZ optimization with
approximate re bond lengths. Calculated and
experimental [1] 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; 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 CF3CF2C(=O)Cl (MHz).
Calculation was made on (1) MP2/6-311+G(3df,3pd) and (2)
MP2/aug-cc-pVTZ optimized molecular structures, each with empirically
derived approximate equilibrium 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 |
- |
49.14 |
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48.90 |
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49.7148(61) |
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Xbb |
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26.28 |
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26.04 |
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25.4688(90) |
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Xcc |
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22.86 |
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22.85 |
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24.2460(66) |
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|Xab| |
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38.75 |
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38.96 |
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37.77(21) |
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RMS |
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0.98 (3.0 %) |
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0.99 (3.0 %) |
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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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42.64 |
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42.63 |
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41.17(15) |
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Xyy |
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22.86 |
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22.85 |
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24.246(7) |
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Xzz |
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65.50 |
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65.48 |
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65.41(15) |
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ETA |
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0.302 |
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0.302 |
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0.2587(24) |
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Øz,a |
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22.89 |
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23.06 |
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22.569(81) |
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Øa,CCl |
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24.29 |
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24.45 |
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Øz,CCl |
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1.39 |
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1.39 |
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Table 2. 37Cl
nqcc's
in CF3CF2C(=O)Cl
(MHz).
Calculation was made on (1) MP2/6-311+G(3df,3pd) and (2)
MP2/aug-cc-pVTZ optimized molecular structures, each with empirically
derived approximate equilibrium 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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38.81 |
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38.62 |
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39.256(11) |
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Xbb |
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20.79 |
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20.61 |
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20.147(16) |
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Xcc |
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18.02 |
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18.01 |
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19.109(12) |
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|Xab| |
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30.46 |
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30.62 |
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29.84(13) |
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RMS |
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0.78 (3.0 %) |
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0.78 (3.0 %) |
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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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33.61 |
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33.60 |
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Xyy |
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18.02 |
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18.01 |
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Xzz |
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51.62 |
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51.61 |
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ETA |
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0.302 |
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0.302 |
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Øz,a |
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22.81 |
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22.98 |
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Øa,CCl |
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24.21 |
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24.37 |
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Øz,CCl |
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1.39 |
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1.39 |
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| Table 3.
Perfluoropropionyl Chloride. Selected structure parameters
(Å and degrees). r(1) = MP2/6-311+G(3df,3pd) and r(2)
=
MP2/aug-cc-pVTZ optimized molecular structures, each with empirically
derived approximate equilibrium bond lengths. Complete
structures are given here in
Z-matrix format. |
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| Cs |
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r(1) |
r(2) |
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ClC(8) |
1.7439 |
1.7450 |
| C(8)O |
1.1843 |
1.1836 |
| C(8)C(1) |
1.5388 |
1.5392 |
| C(1)C(2) |
1.5394 |
1.5397 |
| C(1)C(8)Cl |
111.24 |
111.01 |
| C(1)C(8)O |
124.40 |
124.66 |
| C(2)C(1)C(8) |
112.82 |
112.93 |
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| Table 4.
Perfluoropropionyl Chloride. Rotational Constants (MHz).
CF3CF2C(=O)35Cl
species. r(1) = MP2/6-311+G(3df,3pd) and r(2) =
MP2/aug-cc-pVTZ optimized molecular structures, each with empirically
derived approximate equilibrium bond lengths. |
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r(1) |
r(2) |
Expt. [1] |
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A |
2034.8 |
2036.7 |
2015.71840(19) |
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B |
852.5 |
851.9 |
842.99816(13) |
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C |
763.8 |
763.1 |
755.97374(14) |
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[1] 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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CH3CH2C(=O)Cl |
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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CF3CF2COCl.html |
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Last
Modified 2 Aug 2010 |
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