## Abstract

Upon slow warming of previously photolyzed matrix samples of OCS/Ar, CS_{2}/Ar, OCS/Kr, and OCS/SF_{6} (M/R = 100), the B (B″)→X chemiluminescence of S_{2} is observed, as reported earlier. In addition, two new progressions were recorded, a weak progression between 5580-6890 Å and a stronger one between 6680-8750 Å. With OC^{34}S, the 6680-8750 Å progression displayed isotopic shifts that allow deduction of ν_{00} = 15750±10 cm^{-1}, ω″_{e} = 699 ± 5 cm^{-1}, and ω_{e}x_{e}″ = 2.6 ± 1 cm^{-1}. Similarly, the weaker 5580-6890 Å progression corresponds to ν_{00} = 20870 ± 30 cm^{-1}, ω″ _{e} = 724 ± 6 cm^{-1}, and ω_{e}x″ _{e} = 2.9 ± 1 cm^{-1}, with a less favored, alternative vibrational assignment that gives ν^{00} = 21600 ± 30 cm ^{-1}, ω″_{e} = 731 ± 6 cm^{-1}, and ω_{e}x″_{e} = 2.9 ± 1 cm^{-1}. These spectroscopic parameters point to assignments of the c ^{1}Σ _{g}^{-}→a ^{1}Δ_{g} and A′ ^{3}Δ_{u} → X ^{3}Σ_{g} ^{-} transitions of S_{2} for the 6680-8750 Å and 5580-6890 Å emissions, respectively. These are the first observations of these transitions of diatomic sulfur, and one of them provides the first direct spectroscopic information illustrating that the c ^{1}Σ _{u}^{-}l state (T_{0} = 20250 ± 200 cm ^{-1}) actually lies lower than the A ^{3}Σ _{u}^{+} and A′ ^{3}Δ_{u} states, as is the case for O_{2}.

Original language | English |
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Pages (from-to) | 692-698 |

Number of pages | 7 |

Journal | The Journal of chemical physics |

Volume | 70 |

Issue number | 2 |

DOIs | |

State | Published - 1 Jan 1979 |