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Spectroscopic analysis uncovers wide lifetime variations across electronic states in diatomic sulfur, indicating strong homogeneous quantum interactions.
Fluorescence decay rates were measured for individual rovibronic spin levels of the B 3Σ−u and B″3Πu states of diatomic sulfur (S2) in a supersonic free jet. The radiative lifetimes of the B 3Σ−u and B″3Πu states were found to be strongly dependent on the spin and vibrational quantum numbers, and fall in the range of 34.2 to 49.3 and 108 to 3888 ns, respectively. The marked variation of the lifetimes was interpreted satisfactorily in terms of the homogeneous interactions between the B 3Σ−u and B″3Πu states. A quantitative deperturbation treatment of both the spectroscopic and lifetime data leads to the evaluation of interaction strengths between the B 3Σ−u and B″ 3Πu states.
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Matsumi et al. (1985) studied this question.
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