|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
H2S |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Deuterium and Sulfur |
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
|
in Hydrogen Sulfide |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Deuterium nqcc's in hydrogen sulfide were measured by Viswanathan
and Dyke [1] and DeLucia and Cederberg [2]. Sulfur-33 nqcc's were
measured by Saleck, Tanimoto, Belov, Klaus, and Winnewisser [3] and Burrus
and Gordy [4]. Edwards, Moncur, and Synder [5] determined an equilibrium
molecular structure. |
|
|
|
|
|
|
|
|
|
|
|
|
Calculation was made here of the deuterium
and sulfur nqcc's on the equilibrium structure. These are compared
with the experimental values in Tables 1 and 2. |
|
|
|
|
|
|
|
|
|
|
|
|
In Tables 1 and 2, 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 model for calculation of the nqcc's,
B3LYP/6-31G(df,3p) for deuterium, and B3LYP/6-311G(3df,3p) and B3LYP/TZV+(3df,3p)
for sulfur. |
|
|
|
|
|
|
|
|
|
|
|
|
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 b-axis is coincident with the twofold
symmetry axis. The nqcc y-axis is chosen coincident with the inertia
c-axis, these are perpendicular to the plane of the molecule. Ø
(degrees) is the angle between its subscripted parameters. ETA = (Xxx
- Xyy)/Xzz. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 1. Deuterium nqcc's
in D2S (kHz). |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. [1] |
|
| |
|
|
|
|
|
|
|
|
2H |
Xaa |
|
52.8 |
|
51.84(17) |
|
|
|
Xbb |
|
36.6 |
|
36.54(13) |
|
|
|
Xcc |
|
- 89.4 |
|
- 88.38(11) |
|
|
|
Xab |
± |
109.3 |
± |
109.24(31) |
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
0.8 (1.4 %) |
|
|
|
|
|
RSD |
|
1.1 (0.9 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
- 64.9 |
|
- 65.32(31) |
|
|
|
Xyy |
|
- 89.4 |
|
- 88.38(11) |
|
|
|
Xzz |
|
154.3 |
|
153.70(31) |
|
|
|
ETA |
|
0.159 |
|
|
|
|
|
Øz,b |
|
47.11 |
|
|
|
|
|
Øb,SD |
|
46.06 |
|
|
|
|
|
Øz,SD |
|
1.06 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
Table 2. 33S nqcc's
in H2S (MHz). |
|
|
|
|
|
|
|
|
|
|
|
|
Calc [a] B3LYP/6-311G(3df,3p) |
|
|
|
Calc [b] B3LYP/TZV+(3df,3p) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Calc. [a]
|
|
Calc. [b] |
|
Expt. [3] |
|
| |
|
|
|
|
|
|
|
|
|
Xaa |
- |
33.37 |
- |
33.36 |
- |
32.820(53) |
|
|
Xbb |
|
- 7.98 |
|
- 8.00 |
|
- 8.597(66) |
|
|
Xcc |
|
41.35 |
|
41.36 |
|
41.416(56) |
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
0.48 (1.7 %) |
|
0.47 (1.7 %) |
|
|
|
|
RSD |
|
0.39 (1.7 %) |
|
0.35 (1.5 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Structure parameters, re [5] |
SH = 1.3356 Å |
|
|
|
|
|
|
HSH = 92.12o |
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
|
[1] R.Viswanathan and T.R.Dyke, J.Mol.Spectrosc. 103,231(1984). |
|
|
[2] F.C.DeLucia and J.W.Cederberg, J.Mol.Spectrosc. 40,52(1971). |
|
|
[3] A.H.Saleck, M.Tanimoto, S.P.Belov, Th.Klaus, and G.Winnewisser,
J.Mol.Spectrosc. 62,1429(1987). |
|
|
[4] C.A.Burrus and W.Gordy, Phys.Rev. 92,274(1953). |
|
|
[5] T.H.Edwards, N.K.Moncur, and L.E.Synder, J.Chem.Phys. 46,2139(1967). |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
H2O |
H2CO |
H2CS |
SH3+ |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents |
|
|
|
|
|
Molecules/Deuterium |
|
|
|
|
|
Molecules/Sulfur |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
H2S.html |
|
|
|
|
|
|
Last
Modified 26 Sept 2004 |
|
|
|
|
|
|
|
|
|
|