Journal article
An ab initio study of the low-lying electronic states of S 3
The Journal of chemical physics, Vol.125(8), pp.084314-084314-8
08/28/2006
Handle:
https://hdl.handle.net/2376/112192
PMID: 16965019
Abstract
Accurate calculations of the low-lying singlet and triplet electronic states of thiozone,
S
3
, have been carried out using large multireference configuration interaction wave functions. Cuts of the full potential energy surfaces along the stretching and bending coordinates have been presented, together with the vertical excitation spectra. The strong experimentally observed absorption around
395
nm
is assigned to the
1
B
2
1
state, which correlates to ground state products. Absorption at wavelengths shorter than
260
nm
is predicted to lead to singlet excited state products,
S
2
(
a
Δ
g
1
)
+
S
(
D
1
)
. The spectroscopic properties of the
X
Σ
g
−
3
,
a
Δ
g
1
, and
b
Σ
g
+
1
electronic states of the
S
2
radical have also been accurately characterized in this work. The investigations of the low-lying electronic states were accompanied by accurate ground state coupled cluster calculations of the thermochemistry of both
S
2
and
S
3
using large correlation consistent basis sets with corrections for core-valence correlation, scalar relativity, and atomic spin-orbit effects. Resulting values for
D
0
(
S
2
+
S
)
and
∑
D
0
for
S
3
are predicted to be 61.3 and
162.7
kcal
∕
mol
, respectively, with conservative uncertainties of
±
1
kcal
∕
mol
. Analogous calculations predict the
C
2
v
-
D
3
h
(open-cyclic) isomerization energy of
S
3
to be
4.4
±
0.5
kcal
∕
mol
.
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Details
- Title
- An ab initio study of the low-lying electronic states of S 3
- Creators
- Kirk Peterson - Department of Chemistry, Washington State University, Pullman, Washington 99164-4630James Lyons - Institute of Geophysics and Planetary Physics, University of California at Los Angeles, Los Angeles, California 90095Joseph Francisco - Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393 and Department of Earth and Atmospheric Sciences, Purdue University, West Lafayette, Indiana 47907-1393
- Publication Details
- The Journal of chemical physics, Vol.125(8), pp.084314-084314-8
- Academic Unit
- Chemistry, Department of
- Publisher
- American Institute of Physics
- Identifiers
- 99900547683801842
- Resource Type
- Journal article