### 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 ^{1}B _{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 ^{1}Δ _{g}) +S( ^{1}D). The spectroscopic properties of the X ^{3}σ _{g}
^{-}, a ^{1}Δ _{g}, and b ^{1}σ _{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 language | English (US) |
---|---|

Article number | 084314 |

Journal | Journal of Chemical Physics |

Volume | 125 |

Issue number | 8 |

DOIs | |

State | Published - Sep 8 2006 |

Externally published | Yes |

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### ASJC Scopus subject areas

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

### Cite this

_{3}

*Journal of Chemical Physics*,

*125*(8), [084314]. https://doi.org/10.1063/1.2222367

**An ab initio study of the low-lying electronic states of S _{3}
.** / Peterson, Kirk A.; Lyons, James; Francisco, Joseph S.

Research output: Contribution to journal › Article

_{3}',

*Journal of Chemical Physics*, vol. 125, no. 8, 084314. https://doi.org/10.1063/1.2222367

_{3}Journal of Chemical Physics. 2006 Sep 8;125(8). 084314. https://doi.org/10.1063/1.2222367

}

TY - JOUR

T1 - An ab initio study of the low-lying electronic states of S 3

AU - Peterson, Kirk A.

AU - Lyons, James

AU - Francisco, Joseph S.

PY - 2006/9/8

Y1 - 2006/9/8

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

VL - 125

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 8

M1 - 084314

ER -