An ab initio study of the low-lying electronic states of S 3

Kirk A. Peterson, James R. Lyons, Joseph S. Francisco

Research output: Contribution to journalArticle

39 Scopus citations

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 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.

Original languageEnglish (US)
Article number084314
JournalJournal of Chemical Physics
Volume125
Issue number8
DOIs
StatePublished - Sep 8 2006
Externally publishedYes

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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