|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
t-ClHC=CHNO |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Chlorine |
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
in t-1-Chloro-2-Nitrosoethene
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Chlorine nqcc's in t-1-chloro-2-nitrosoethene, and partial
ro structures were determined by Sakaizumi et al. [1]. Calculation of the nqcc's was made here on
these structures (designated Sets I and II). The results are compared with
the experimental nqcc's in Table 1. Neither the structures nor the nqcc's are accurately determined. |
|
|
|
|
|
|
|
|
|
|
|
|
The data in Table 1 is seen to suggest
that the experimental Xbb and Xcc
should be reversed.
However, nqcc's calculated on structures optimized at the
B3P86/6-311+G(3d,3p)
and MP2/6-311+G(3d,3p) levels of theory are in qualitative agreement
with the experimental nqcc's. These nqcc's are compared in Table
2. |
|
|
|
|
|
|
|
|
|
|
|
|
Molecular structure
parameters are compared in Table 3. Rotational constants are compared in Table 4. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
Table 1. Chlorine
nqcc's in t-ClHC=CHNO (MHz). Calculation was made on the partial
ro structures of Sakaizumi et al. [1]. |
|
| |
|
|
|
|
|
|
|
|
|
35Cl
|
|
Calc/Set I
|
|
Calc/Set II |
|
Expt. [1] |
|
| |
|
|
|
|
|
|
|
|
|
Xaa |
- |
52.63 |
- |
53.36 |
- |
50.4(21) |
|
|
Xbb |
|
22.90 |
|
22.97 |
|
31.1(63) |
|
|
Xcc |
|
29.73 |
|
30.39 |
|
19.3(84) |
|
|
|Xab| |
|
45.89 |
|
46.07 |
|
|
|
|
|
|
|
|
|
|
|
|
|
37Cl
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Xaa |
- |
41.62 |
- |
42.19 |
- |
40.9(10) |
|
|
Xbb |
|
18.18 |
|
18.24 |
|
27.7(22) |
|
|
Xcc |
|
23.43 |
|
23.95 |
|
13.2(32) |
|
|
|Xab| |
|
36.05 |
|
36.19 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
Table 2. Chlorine
nqcc's in t-ClHC=CHNO (MHz). Calculation was made on structures optimized at the B3P86/6-311+G(3d,3p)
and MP2/6-311+G(3d,3p) levels of theory. |
|
| |
|
|
|
|
|
|
|
|
|
35Cl
|
|
Calc/B3P86
|
|
Calc/MP2 |
|
Expt. [1] |
|
| |
|
|
|
|
|
|
|
|
|
Xaa |
- |
55.88 |
- |
55.65 |
- |
50.4(21) |
|
|
Xbb |
|
29.40 |
|
28.92 |
|
31.1(63) |
|
|
Xcc |
|
26.48 |
|
26.73 |
|
19.3(84) |
|
|
|Xab| |
|
38.19 |
|
39.12 |
|
|
|
|
|
|
|
|
|
|
|
|
|
37Cl
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Xaa |
- |
44.13 |
- |
43.96 |
- |
40.9(10) |
|
|
Xbb |
|
23.26 |
|
22.89 |
|
27.7(22) |
|
|
Xcc |
|
20.87 |
|
21.07 |
|
13.2(32) |
|
|
|Xab| |
|
30.00 |
|
30.73 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
| Table 3. Molecular structure parameters, partial ro and ab initio (Å and degrees). |
|
|
|
|
|
| |
# Assumed value. |
|
|
| Z-Matrix |
Set I [1] |
Set II [1] |
B3P86 |
MP2 |
|
|
|
|
|
| C(1)Cl |
1.716(5) |
1.726 # |
1.698 |
1.705 |
C(1)H
|
1.080 # |
1.080 # |
1.081 |
1.080 |
| C(1)=C(2) |
1.320(5) |
1.310(5) |
1.335 |
1.343 |
| C(2)H |
1.089 # |
1.089 # |
1.084 |
1.083 |
| C(2)N |
1.434 # |
1.434 # |
1.410 |
1.414 |
| N=O |
1.220 # |
1.220 # |
1.212 |
1.236 |
| ClC(1)C(2) |
123.0(5) |
123.0(5) |
123.7 |
123.4 |
| HC(1)C(2) |
123.0 # |
123.0 # |
120.9 |
120.8 |
| C(1)C(2)H |
121.0 # |
121.0 # |
125.7 |
125.8 |
| C(1)C(2)N |
116.1 # |
116.1(5) |
115.0 |
114.7 |
| C(2)N=O |
112.90 # |
112.90 # |
113.8 |
113.0 |
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
| Table 4. Rotational Constants (MHz). 35Cl
Species. |
| |
|
|
|
|
|
|
B3P86 ropt |
MP2 ropt |
Expt. [1] |
|
|
|
|
|
|
A |
40 170 |
39 008 |
38 935(147) |
|
B |
1 530.2 |
1 518.3 |
1 519.056(6) |
|
C |
1 474.0 |
1 461.5 |
1 461.596(6) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
[1] T.Sakaizumi, M.Nishikawa, and O.Ohashi,
J.Mol.Spectrosc. 178,113(1996). |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
H2C=CHCl |
t-FHC=CHCl |
H2C=CFCl |
|
|
|
F2C=CHCl |
c-FHC=CHCl |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents |
|
|
|
|
|
Molecules/Chlorine |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
ClCHCHNO.html |
|
|
|
|
|
|
Last
Modified 20 Feb 2005 |
|
|
|
|
|
|
|
|
|
|