TY - JOUR
T1 - An ab initio study of the low-lying electronic states of S 3
AU - Peterson, Kirk A.
AU - Lyons, James R.
AU - Francisco, Joseph S.
N1 - Copyright:
Copyright 2011 Elsevier B.V., All rights reserved.
PY - 2006
Y1 - 2006
N2 - 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 1B 2 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 1Δ g) +S( 1D). The spectroscopic properties of the X 3σ g -, a 1Δ g, and b 1σ g + 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 σD 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 2v-D 3h (open-cyclic) isomerization energy of S 3 to be 4.4±0.5 kcal/mol.
AB - 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 1B 2 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 1Δ g) +S( 1D). The spectroscopic properties of the X 3σ g -, a 1Δ g, and b 1σ g + 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 σD 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 2v-D 3h (open-cyclic) isomerization energy of S 3 to be 4.4±0.5 kcal/mol.
UR - http://www.scopus.com/inward/record.url?scp=33748251058&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=33748251058&partnerID=8YFLogxK
U2 - 10.1063/1.2222367
DO - 10.1063/1.2222367
M3 - Article
AN - SCOPUS:33748251058
SN - 0021-9606
VL - 125
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 8
M1 - 084314
ER -