|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
CF2Cl-C(=O)-CF2Cl |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Chlorine |
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
in
1,3-Dichlorotetrafluoroacetone
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Calculations of the chlorine nqcc's
in 1,3-dichlorotetrafluoroacetone were made on structures given by
MP2/6-311+G(3df) optimization with
approximate re C-C, CF, and
C=O, and CCl
bond lengths and by MP2/aug-cc-pVTZ
optimization with approximate re
C-C, CF, and
C=O, and CCl
bond lengths. These
calculated nqcc's are compared with experimental values in Tables 1 -
3. Structure
parameters are given in Table 4, rotational constants in Table 5.
|
|
|
|
|
|
|
|
|
|
|
|
|
In Tables 1 - 3, subscripts a,b,c
refer to the
principal axes of the inertia tensor; x,y,z to the principal axes
of the nqcc tensor.
Øz,CCl (degrees) is the angle between the z-principal
axis and the CCl axis. ETA = (Xxx - Xyy)/Xzz. |
|
|
RMS is the root mean square
difference between calculated and experimental diagonal nqcc's (percent
of the average of the magnitudes of experimental nqcc's). RSD is
the residual standard
deviation of the model for calculation of the nqcc's, which may be
taken as an estimate of uncertainty in the calculated nqcc's (not
taking into consideration inaccuracies in the structure parameters). |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
|
Table 1. 35Cl
nqcc's in CF235Cl-C(=O)-CF235Cl
(MHz).
Calculation was made on structures
given by
(1) MP2/6-311+G(3df) optimization,
and (2) MP2/aug-cc-pVTZ optimization; each with approximate re
bond lengths. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
|
|
Calc (1) |
|
Calc (2) |
|
Expt [1] |
|
| |
|
|
|
|
|
|
|
|
|
|
35Cl |
Xaa |
|
- 0.72 |
|
- 0.49 |
|
- 0.1423(43) |
|
|
|
Xbb |
- |
32.40 |
- |
32.56 |
- |
32.2303(53) |
|
|
|
Xcc |
|
33.12 |
|
33.05 |
|
32.3726(31) |
|
|
|
Xab |
- |
50.76 |
- |
50.56 |
- |
51.62(45) |
|
|
|
Xac |
± |
15.60 |
± |
15.57 |
± |
13.6938(41) |
|
|
|
Xbc |
± |
18.62 |
± |
18.65 |
± |
19.44(15) |
|
|
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
0.56 (2.6 %) |
|
0.48 (2.2 %) |
|
|
|
|
|
RSD |
|
0.49 (1.1 %) |
|
0.49 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
35.80 |
|
35.70 |
|
36.1(8) |
|
|
|
Xyy |
|
39.37 |
|
39.30 |
|
37.7(1) |
|
|
|
Xzz |
- |
75.17 |
- |
75.01 |
- |
73.7(8) |
|
|
|
ETA |
|
0.0475 |
|
0.0480 |
|
0.02(1) |
|
|
|
Øz,CCl |
|
1.66 |
|
1.72 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
|
Table 2. Cl
nqcc's in CF235Cl-C(=O)-CF237Cl
(MHz).
Calculation was made on structures
given by (1) MP2/6-311+G(3df) optimization
and (2) MP2/aug-cc-pVTZ optimization, each with approximate re
bond lengths. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
|
|
Calc (1) |
|
Calc (2) |
|
Expt |
|
| |
|
|
|
|
|
|
|
|
|
|
35Cl |
Xaa |
|
- 1.71 |
|
- 1.47 |
|
|
|
|
|
Xbb |
- |
30.41 |
- |
30.56 |
|
|
|
|
|
Xcc |
|
32.12 |
|
32.04 |
|
|
|
|
|
Xab |
- |
50.65 |
- |
50.45 |
|
|
|
|
|
Xac |
|
17.10 |
|
17.05 |
|
|
|
|
|
Xbc |
|
20.09 |
|
20.12 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
|
|
|
|
|
|
|
|
RSD |
|
0.49 (1.1 %) |
|
0.49 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
37Cl |
Xaa |
|
- 1.54 |
|
- 1.36 |
|
|
|
|
|
Xbb |
- |
25.28 |
- |
25.41 |
|
|
|
|
|
Xcc |
|
26.83 |
|
26.77 |
|
|
|
|
|
Xab |
- |
40.60 |
- |
40.44 |
|
|
|
|
|
Xac |
- |
11.43 |
- |
11.41 |
|
|
|
|
|
Xbc |
- |
13.21 |
- |
13.24 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
|
|
|
|
|
|
|
|
RSD |
|
0.44 (1.1 %) |
|
0.44 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
|
Table 3. 37Cl
nqcc's in CF237Cl-C(=O)-CF237Cl
(MHz).
Calculation was made on structures
given by
(1) MP2/6-311+G(3df) optimization,
and (2) MP2/aug-cc-pVTZ optimization; each with approximate re
bond lengths. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
|
|
Calc (1) |
|
Calc (2) |
|
Expt |
|
| |
|
|
|
|
|
|
|
|
|
|
37Cl |
Xaa |
|
- 2.31 |
|
- 2.13 |
|
|
|
|
|
Xbb |
- |
23.80 |
- |
23.92 |
|
|
|
|
|
Xcc |
|
26.10 |
|
26.05 |
|
|
|
|
|
Xab |
- |
40.51 |
- |
40.36 |
|
|
|
|
|
Xac |
± |
12.61 |
± |
12.58 |
|
|
|
|
|
Xbc |
± |
14.40 |
± |
14.43 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
|
|
|
|
|
|
|
|
RSD |
|
0.44 (1.1 %) |
|
0.44 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
28.21 |
|
28.14 |
|
|
|
|
|
Xyy |
|
31.03 |
|
30.98 |
|
|
|
|
|
Xzz |
- |
59.24 |
- |
59.12 |
|
|
|
|
|
ETA |
|
0.0475 |
|
0.0480 |
|
|
|
|
|
Øz,CCl |
|
1.66 |
|
1.72 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 4. CF2Cl-C(=O)-CF2Cl.
Selected structure parameters (Å and degrees).
r(1) = MP2/6-311+G(3df)
optimization, and r(2) = MP2/aug-cc-pVTZ optimization, each with
approximate re bond lengths.
Complete
structures are given here in
Z-matrix
format. |
| |
|
|
|
| Point Group C2 |
|
r(1) |
r(2) |
|
|
|
|
|
C(1)O |
1.1944 |
1.1944 |
| C(1)C(3) |
1.5413 |
1.5408 |
| C(1)C(4) |
1.5413 |
1.5408 |
| C(3,4)Cl |
1.7591 |
1.7586 |
| C(3)C(1)C(4) |
117.10 |
117.17 |
| C(3)C(1)O |
121.45 |
121.42 |
| C(4)C(1)O |
121.45 |
121.42 |
| C(1)C(3,4)Cl |
108.25 |
108.11 |
| ClC(3,4)C(1)O |
93.27 |
93.38 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 5. CF235Cl-C(=O)-CF235Cl.
Rotational Constants (MHz). r(1) = MP2/6-311+G(3df)
optimization
and r(2) = MP2/aug-cc-pVTZ optimization, each with approximate re
bond lengths. |
| |
|
|
|
|
|
|
r(1) |
r(2) |
Expt [1] |
|
|
|
|
|
|
A |
1539.3 |
1539.8 |
1535.29390(26) |
|
B |
723.1 |
723.8 |
713.75756(38) |
|
C |
694.9 |
695.4 |
687.04713(40) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
[1] G.Kadiwar, C.T.Dewberry,
G.S.Grubbs II, and S.A.Cooke, Abstract RH11, 65th OSU International
Symposium on Molecular Spectroscopy, 2010. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
CF2Cl-C(=O)-CF3 |
CH2Cl-C(=O)-CH3 |
CH2Cl-C(=O)-CH2Cl |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents |
|
|
|
|
|
Molecules/Chlorine |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
CF2ClCOCF2Cl.html |
|
|
|
|
|
|
Last
Modified 10 July 2010 |
|
|
|
|
|
|
|
|
|
|