|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
1,4-Thiazine and Phenothiazine
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Nitrogen and Sulfur
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
|
in 1,4-Thiazine and Phenothiazine
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Calculation of nitrogen
and
sulfur nqcc tensors in thiazine and in phenothiazine
was made on molecular structures given by B3P86/6-31G(3d,3p)
optimization. These are given in Tables 1 and 2. Structure
parameters are
compared in Table 3. Rotational constants and electric dipole
moments are given in Table 4.
|
|
|
|
|
|
|
|
|
|
|
|
|
1,4-Thiazine
|
|
Phenothiazine
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
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. ETA = (Xxx
- Xyy)/Xzz. |
|
|
RSD is the residual standard deviation
of calibration of the B3PW91/6-311+G(df,pd) model for calculation of
the 14N efg's/nqcc's; and B3LYP/6-311G(3df,3p) and B3LYP/TZV+(3df,3p) models for calculation of
the 33S efg's/nqcc's. |
|
|
Note: Due to the C2V symmetry of the molecules, 14N nqcc tensors are the same in 32S and 33S
species. Also, in 1,4-thiazine, N and S lie on a-axis, whereas in
phenothiazine, these lie on b-axis. This explains the apparent
discrepancy between Xaa and Xbb in Tables 1 and 2.
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 1. Nitrogen
nqcc tensors in 1,4-Thiazine and Phenothiazine (MHz). Calculation was made
on the B3P86/6-31G(3d,3p) ropt structures.
|
|
| |
|
|
|
|
|
|
|
|
|
|
1,4-Thiazine
|
Phenothiazine
|
|
| |
|
|
|
|
|
|
|
|
14N |
Xaa (xx)
|
|
2.331
|
|
2.567
|
|
|
|
Xbb (yy)
|
|
2.580
|
|
2.251
|
|
|
|
Xcc (zz)
|
-
|
4.911
|
-
|
4.818
|
|
|
|
ETA
|
|
0.0508
|
-
|
0.0654
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
0.030 (1.3 %) |
|
0.030 (1.3 %) |
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 2. Sulfur
nqcc tensors in 1,4-Thiazine and Phenothiazine (MHz). Calculation was made
on the B3P86/6-31G(3d,3p) ropt structures.
|
|
| |
|
|
|
|
|
|
|
|
B3LYP/6-311G(3df,3p)
|
1,4-Thiazine
|
Phenothiazine
|
|
| |
|
|
|
|
|
|
|
|
33S |
Xaa (xx)
|
|
- 7.67
|
-
|
35.82
|
|
|
|
Xbb (yy)
|
-
|
36.87
|
|
- 5.51
|
|
|
|
Xcc (zz)
|
|
44.56
|
|
41.33
|
|
|
|
ETA
|
|
0.656
|
-
|
0.733
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
0.39 (1.7 %) |
|
0.39 (1.7 %)
|
|
|
|
|
|
|
|
|
|
|
B3LYP/TZV+(3df,3p)
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
33S |
Xaa (xx) |
|
- 7.76
|
-
|
35.98 |
|
|
|
Xbb (yy) |
-
|
36.94
|
|
- 5.56 |
|
|
|
Xcc (zz) |
|
44.70
|
|
41.54 |
|
|
|
ETA
|
|
0.653
|
-
|
0.732 |
|
|
|
|
|
|
|
|
|
|
|
RSD
|
|
0.35 (1.5 %) |
|
0.35 (1.5 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
Table 3. Selected molecular structure parameters, B3P86/6-31G(3d,3p) ropt (Å and degrees). Complete structures are given here in Z-matrix format.
|
| |
|
|
|
|
|
|
1,4-Thiazine |
Phenothiazine |
|
|
|
SC
|
1.7748
|
1.7643
|
| CSC |
98.10
|
102.84
|
| NC |
1.3894
|
1.3851
|
NH
|
1.0019
|
1.0064
|
CNC
|
121.43
|
127.28
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
Table 4. Rotational Constants (MHz) and Electric Dipole Moments (D), 32S species.
|
| |
|
|
|
|
|
|
|
1,4-Thiazine |
Phenothiazine |
|
|
|
|
|
|
|
A
|
5153.0
|
1674.4
|
|
|
B
|
3354.0
|
432.9
|
|
|
C
|
2031.7
|
343.9
|
|
|
|
|
|
|
|
|µa|
|
3.0
|
|
|
|
|µb|
|
|
2.0
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Thiophene
|
Pyridine
|
Thiazole
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents |
|
|
|
|
|
Molecules/Nitrogen |
|
|
|
|
|
Molecules/Sulfur |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Thiazine.html |
|
|
|
|
|
|
Last
Modified 1 Dec 2013 |
|
|
|
|
|
|
|
|
|
|