Photodissociation dynamics of small polyatomics: Isolated molecule behavior and collision induced effects

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Abstract
We outline a conceptually simple theoretical approach to the study of photodissociation of small polyatomics at low pressures. In this approach, we employ a realistic Hamiltonian and solve numerically for the ensuing dynamics. Formaldehyde is treated as a prototype, and the results of calculations are given and compared with recent experiments. Several conclusions are drawn about the photodissociation mechanism. In particular, our calculations suggest that the barrier to products lies above the first few vibrational levels of S1. Hence, both the experimentally determined nonradiative decay of S1, and the much slower CO appearance rate, must be collision induced. We expect similar time‐lag behavior to be evinced in other small polyatomics and we suggest that collisional effects often may persist to very low pressure.
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