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CF3-CF2Cl |
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in
Perfluoroethyl Chloride
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Calculation of the chlorine nqcc
tensor in perfluoroethyl chloride was made on a
molecular structure given by MP2/aug-cc-pVTZ
optimization (ropt),
and on same structure but with ~re CCl,
C-C, and CF bond lengths.
(Also, see Calculation of Nuclear
Quadrupole Coupling Constants on Approximate Equilibrium Structures:
Ethanes.)
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Calculated nqcc tensors are compared
with experimental values [1]
in Tables 1 and 2.
Structure
parameters are given in Table 3. Rotational constants and dipole
moments (given by B1LYP/TZV(3df,2p) calculation) are given in Tables 4
and 5. Quartic centrifugal distortion constants, calculated and
experimental, are given in Table 6. |
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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.
Ø (degrees) is the angle between its subscripted
parameters. ETA = (Xxx - Xyy)/Xzz. |
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RMS is root mean square difference
between calculated and experimental diagonal nqcc's. RSD is the
calibration residual
standard deviation of
the B1LYP/TZV(3df,2p) model for calculation of the chlorine nqcc's. |
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Table 1. 35Cl
nqcc's in
CF3-CF2Cl (MHz).
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ropt
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~re |
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Expt. [1] |
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Xaa |
- |
25.76 |
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25.76 |
- |
25.7949(19) |
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Xbb |
- |
13.24 |
- |
13.00 |
- |
12.8998(29) |
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Xcc |
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39.00 |
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38.77 |
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38.6937(22) |
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|Xab| |
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57.49 |
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57.08 |
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56.90(20) |
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RMS |
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0.26 (1.0 %) |
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0.08 (0.3 %) |
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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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38.34 |
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38.06 |
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Xyy |
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39.00 |
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38.77 |
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Xzz |
- |
77.33 |
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76.82 |
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76.61(20) |
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ETA |
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0.008 |
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0.009 |
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Øz,a |
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41.89 |
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41.81 |
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Øa,CCl |
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43.16 |
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43.13 |
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Øz,CCl |
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1.26 |
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1.32 |
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Table 2. 37Cl nqcc's in
CF3-CF2Cl (MHz).
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ropt
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~re |
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Expt. [1] |
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Xaa |
- |
22.22 |
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22.21 |
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22.2210(33) |
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Xbb |
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- 8.51 |
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- 8.34 |
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- 8.2762(48) |
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Xcc |
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30.74 |
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30.55 |
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30.4972(35) |
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|Xab| |
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45.06 |
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44.73 |
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45.09(42) |
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RMS |
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0.19 (1.0 %) |
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0.05 (0.2 %) |
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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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30.21 |
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29.99 |
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Xyy |
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30.74 |
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30.55 |
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Xzz |
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60.95 |
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60.54 |
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ETA |
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0.008 |
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0.009 |
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Øz,a |
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40.68 |
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40.60 |
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Øa,CCl |
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41.94 |
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41.92 |
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Øz,CCl |
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1.26 |
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1.32 |
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| Table 3. CF3-CF2Cl.
Selected structure
parameters (Å and degrees). Complete structures are given here in Z-matrix format. |
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| CS |
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ropt |
~re |
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C(2)Cl |
1.7500 |
1.7467 |
| C(2)F(4,5) |
1.3371 |
1.3311 |
| C(2)C(3) |
1.5467 |
1.5435 |
| C(3)C(2)Cl |
111.01 |
111.01 |
| C(3)C(2)F(4,5) |
108.44 |
108.44 |
| FC(2)F |
108.50 |
108.50 |
| F(4,5)C(2)Cl |
110.18 |
110.18 |
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| Table 4. CF3-CF235Cl
Equilibrium Rotational Constants (MHz) and Dipole Moments (D). |
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ropt |
~re |
Expt. [1] |
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A |
2348.94 |
2367.26 |
2355.757034(98) |
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B |
1530.02 |
1539.12 |
1526.04449(10) |
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C |
1378.09 |
1385.78 |
1375.08171(12) |
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|mua| |
0.47 |
0.45 |
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|mub| |
0.36 |
0.34 |
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mutot |
0.60 |
0.57 |
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| Table 5. CF3-CF237Cl
Equilibrium
Rotational Constants (MHz) and Dipole Moments (D). |
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ropt |
~re |
Expt. [1] |
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A |
2337.65 |
2355.86 |
2344.36431(46) |
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B |
1502.64 |
1511.52 |
1498.75959(22) |
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C |
1352.06 |
1359.57 |
1349.11638(21) |
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|mua| |
0.48 |
0.46 |
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|mub| |
0.35 |
0.33 |
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mutot |
0.60 |
0.57 |
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| Table 6. CF3-CF235Cl
Quartic Centrifugal Distortion Constants (kHz). |
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B3LYP * |
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Expt [1] |
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Delta_J |
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0.120 |
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0.1224(10) |
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Delta_KJ |
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0.0460 |
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0.0666(25) |
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Delta_K |
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0.134 |
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0.1505(17) |
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delta_J |
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0.0185 |
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0.0199(12) |
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delta_K |
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0.0461 |
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* Run B3LYP/cc-pVTZ opt
output=pickett ---> extract the principal axes structure --->
then B3LYP/cc-pVTZ freq=vibrot output=pickett. Doug Fox, Gaussian
Inc., private communication. |
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[1] B.E.Long, G.S.Grubbs
II, J.Langridge, and S.A.Cooke, J.Mol.Struct. 1023,55(2012);
B.E.Long,
J.Langridge,
S.A.Cooke, and G.S.Grubbs II, 66th International Symposium
on
Molecular Spectroscopy, Ohio State University, 2011, Abstract RH03. |
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CHF2-CHFCl |
CHF2-CH2Cl |
CHF2-CF2Cl |
CH2F-CF2Cl |
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|
Calculation
of Nuclear Quadrupole Coupling Constants on Approximate Equilibrium Structures: Ethanes |
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Table of Contents |
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Molecules/Chlorine |
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CF3CF2Cl.html |
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Last
Modified 7 Oct 2012 |
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