Abstract

The collisional deactivation of the laser excited states A 2Σ+(v′ = 1, N′ = 4, 12) of OH in a flame is studied by measurement of spectrally resolved fluorescence decays in the picosecond time domain. Quenching and depolarization rates, as well as vibrational energy-transfer (VET) and rotational energy-transfer (RET) rates are determined. An empirical model describes the temporal evolution of the quenching and VET rates that emerge from the rotational-state relaxation. Fitting this model to the measured 1–0 and 0–0 fluorescence decays yields the quenching and VET rates of the initially excited rotational state along with those that correspond to a rotationally equilibrated vibronic-state population. VET from the higher rotational state (N′ = 12) shows a tendency for resonant transitions to energetic close-lying levels. RET is investigated by analysis of the temporal evolution of the 1–1 emission band. The observed RET is well described by the energy-corrected sudden-approximation theory in conjunction with a power-gap law.

© 1998 Optical Society of America

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