Abstract
In order to adequately describe rotation of photofragments and dynamics of vector correlations in liquids, we have generalized the J-diffusion model by allowing the rotational relaxation rate to be angular momentum dependent. The calculated nonequilibrium rotational correlation functions (CFs) are shown to decay much slower than their equilibrium counterparts, and orientational CFs of hot photofragments exhibit coherent behavior, which persists for several rotational periods. In practical terms, the standard and generalized J-diffusion models are shown to be almost indistinguishable under equilibrium conditions. Far from equilibrium, their predictions may differ dramatically.
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