Fluorescence lifetimes of single vibrational levels in HSO (Ã 2A′)

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Abstract
Fluorescence lifetimes of single vibrational levels of the first excited state of HSO and DSO have been measured under effusive flow conditions following excitation by a pulsed dye laser. The lifetimes show a systematic decrease with v′3 (S–O stretch) from 74 μs (v′3=1) to 26 μs (v′3=8) for HSO. For DSO, the lifetimes are longer than the corresponding ones of HSO. These results are interpreted in terms of a second‐order coupling model (Ã 2A′→X 2A′′→continuum) in which the final states are those of H+SO dissociation continuum. An analytical expression is given to compute the vibrational energy dependence of nonradiative rates assuming an energy dependent linewidth from the dissociation.