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t-CF3CF2CF2C(=O)Cl |
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in
Perfluorobutyryl Chloride
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Calculations of the chlorine nqcc's
in perfluorobutyryl chloride were made on structures given by
MP2/6-311+G(d,p) and MP2/6-311+G(2d,p) optimization, each with ~re C-C, CF, and C=O, and CCl
bond lengths. These
calculated nqcc's are shown 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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Table 1. 35Cl
nqcc's in t-CF3CF2CF2C(=O)Cl (MHz).
Calculation was made on structures
given by (1) MP2/6-311+G(d,p), and (2) MP2/6-311+G(2d,p)
optimization, 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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32.86 |
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33.32 |
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33.51(2) |
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Xbb |
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9.75 |
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10.22 |
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9.21(2) |
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Xcc |
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23.11 |
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23.10 |
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24.30(1) |
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|Xab| |
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49.90 |
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49.64 |
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48.8(1) |
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RMS |
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0.84 (3.8 %) |
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0.91 (4.1 %) |
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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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42.70 |
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42.66 |
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41.13(2) |
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Xyy |
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23.11 |
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23.10 |
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24.30(1) |
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Xzz |
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65.81 |
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65.76 |
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65.43(2) |
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ETA |
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0.298 |
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0.297 |
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0.2572(4) |
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Øz,a |
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33.44 |
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33.16 |
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33.185(8) |
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Øa,CCl |
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34.95 |
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34.74 |
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Øz,CCl |
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1.51 |
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1.58 |
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Table 2. 37Cl
nqcc's in t-CF3CF2CF2C(=O)Cl (MHz).
Calculation was made on structures
given by (1) MP2/6-311+G(d,p), and (2) MP2/6-311+G(2d,p)
optimization, each with ~re bond lengths. |
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Calc (1)
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Calc (2) |
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Expt |
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Xaa |
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26.22 |
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26.58 |
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Xbb |
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8.00 |
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8.37 |
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Xcc |
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18.22 |
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18.21 |
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|Xab| |
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39.19 |
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38.99 |
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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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33.65 |
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33.62 |
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Xyy |
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18.22 |
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18.21 |
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Xzz |
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51.87 |
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51.83 |
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ETA |
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0.298 |
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0.297 |
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Øz,a |
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33.20 |
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32.93 |
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Øa,CCl |
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34.72 |
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34.51 |
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Øz,CCl |
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1.51 |
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1.58 |
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| Table 3. Perfluorobutyryl
Chloride. Selected structure parameters (Å and degrees).
r(1) MP2/6-311+G(d,p), and r(2) MP2/6-311+G(2d,p) optimization,
each with ~re bond lengths. Complete structures are given here in Z-matrix format. |
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| Symmetry CS |
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r(1) |
r(2) |
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C(3)C(2) |
1.5392 |
1.5392 |
| C(2)C(1) |
1.5338 |
1.5338 |
| C(1)C(11) |
1.5404 |
1.5404 |
| C(11)=O |
1.1839 |
1.1839 |
| C(11)Cl |
1.7466 |
1.7466 |
| C(3)C(2)C(1) |
115.55 |
115.39 |
| C(2)C(1)C(11) |
112.16 |
111.98 |
| C(1)C(11)=O |
124.93 |
124.93 |
| C(1)C(11)Cl |
110.78 |
110.97 |
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| Table 4. Perfluorobutyryl
Chloride. Rotational Constants (MHz). Normal species.
r(1) MP2/6-311+G(d,p), and r(2) MP2/6-311+G(2d,p) optimization,
each with ~re bond lengths. |
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r(1) |
r(2) |
Expt [1] |
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A |
1420.07 |
1420.51 |
1409.0159(3) |
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B |
484.76 |
484.88 |
478.4600(2) |
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C |
447.80 |
448.27 |
442.1171(1) |
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[1] G.S.Grubbs II and S.A.Cooke,
Chem.Phys.Lett. 483,21(2009). |
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HC(=O)Cl |
FC(=O)Cl |
CH3C(=O)Cl |
(CH3)3CC(=O)Cl |
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HCC-C(=O)Cl |
CH3CH2-C(=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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tCF3CF2CF2COCl.html |
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Last
Modified 16 Oct 2009 |
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