|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
CH2CH2CCl2 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Chlorine |
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
|
in 1,1-Dichlorocyclopropane |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Calculation of the chlorine nqcc's in
1,1-dichlorocyclopropane was made on the substitution structure of
Flygare et al. [1], and on an ropt structure obtained by
MP2/6-311+G(2d,p) optimization. These are compared with the
experimental nqcc's in Tables 1 and 2. Structure parameters are
compared in Table 3. |
|
|
|
|
|
|
|
|
|
|
|
|
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
inertia c-axis, these are perpendicular to the molecular plane.
Ø (degrees) is the angle between its subscripted
parameters. ETA = (Xxx - Xyy)/Xzz. |
|
|
RMS is the root mean square difference
between calculated and experimental diagonal nqcc's (percentage of the
average of the magnitudes of the experimental nqcc's). RSD is the
calibration residual standard deviation for the B1LYP/TZV(3df,2p) model
for calculation of the chlorine nqcc's. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 1. Chlorine
nqcc's in cyclic CH2CH2CCl2 (MHz). Calculation was made on the substitution molecular structure of Flygare et al. [1]. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. [1] |
|
| |
|
|
|
|
|
|
|
|
35Cl |
Xaa |
- |
45.39 |
- |
43.545(5) |
|
|
|
Xbb |
|
5.80 |
|
4.100(10) |
|
|
|
Xcc |
|
39.59 |
|
39.455(5) |
|
|
|
Xab |
± |
50.41 |
± |
51.5(3) |
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
1.45 (5.0 %) |
|
|
|
|
|
RSD |
|
0.49 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
36.74 |
|
37.0(3) |
|
|
|
Xyy |
|
39.59 |
|
39.455(5) |
|
|
|
Xzz |
- |
76.33 |
- |
76.4(3) |
|
|
|
ETA |
|
0.037 |
|
0.032 |
|
|
|
Øz,b |
|
58.46 |
|
57.5 |
|
|
|
Øb,CCl |
|
57.3 |
|
57.3 |
|
|
|
Øz,CCl |
|
1.16 |
|
0.25 |
|
|
|
|
|
|
|
|
|
|
37Cl |
Xaa |
- |
35.77 |
|
|
|
|
|
Xbb |
|
4.57 |
|
|
|
|
|
Xcc |
|
31.20 |
|
|
|
|
|
Xab |
± |
39.73 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
The angle between the two z-axes is larger than
the ClCCl angle. This is typical of the XCl2 dichloride
moiety. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 2. Chlorine
nqcc's in cyclic CH2CH2CCl2 (MHz). Calculation was made on the MP2/6-311+G(2d,p) ropt molecular structure (see below). |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. [1] |
|
| |
|
|
|
|
|
|
|
|
35Cl |
Xaa |
- |
44.25 |
- |
43.545(5) |
|
|
|
Xbb |
|
4.69 |
|
4.100(10) |
|
|
|
Xcc |
|
39.56 |
|
39.455(5) |
|
|
|
Xab |
± |
51.13 |
± |
51.5(3) |
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
0.53 (1.8 %) |
|
|
|
|
|
RSD |
|
0.49 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
36.90 |
|
37.0(3) |
|
|
|
Xyy |
|
39.56 |
|
39.455(5) |
|
|
|
Xzz |
- |
76.46 |
- |
76.4(3) |
|
|
|
ETA |
|
0.035 |
|
0.032 |
|
|
|
Øz,b |
|
57.79 |
|
57.5 |
|
|
|
Øb,CCl |
|
56.67 |
|
56.67 |
|
|
|
Øz,CCl |
|
1.12 |
|
0.8 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
| Table 3. Molecular structure parameters (Å and degrees). Z-Matrix. |
| ropt = MP2/6-311+G(2d,p) optimization with corrected CCl bond length [2]. |
| |
|
|
|
|
|
rs
[1] |
ropt |
|
|
|
|
|
C(1)Cl |
1.734 |
1.7454 |
|
C(1)C(2,3) |
1.532 |
1.4900 |
|
C(2)C(3) |
1.534 |
1.5271 |
|
CH |
1.085 |
1.0820 |
|
HCH |
117.6 |
116.34 |
|
ClC(1)Cl |
114.6 |
113.34 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
[1] W.H.Flygare, A.Narath, and W.D.Gwinn, J.Chem.Phys. 36,200(1962). |
|
|
[2] I.Merke, L.Poteau, G.Wlodarczak, A.Bouddou, and J.Demaison, J.Mol.Spectrosc. 177,232(1996). |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
CH2CH2CHCl |
H2C=CCl2 |
CF2Cl2 |
CH3CCl2CH3 |
|
|
CH2Cl2 |
CH3SiCl2CH3 |
BHCl2 |
SiH2Cl2 |
|
|
SiCl2 |
O=CCl2 |
SCl2 |
SCCl2 |
|
|
Cl2O |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents |
|
|
|
|
|
Molecules/Chlorine |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
CH2CH2CCl2.html |
|
|
|
|
|
|
Last
Modified 1 June 2006 |
|
|
|
|
|
|
|
|
|
|