Generalized Langevin equation approach to reaction dynamics in liquids

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Abstract
A microscopic formulation for the description of reaction dynamics in liquids is presented. The theory is based on a generalized Langevin equation approach and can be carried out at different levels of description. It also properly accounts for the dynamics of recollision events and static structural correlations. Configuration space and phase space versions of the theory are presented and compared. The configuration space theory illustrates how generalized diffusion equations for the description of the chemical relaxation may be derived and shows that the proper treatment of static structural correlations is important. The phase space version of the theory shows how this formulation may be used to derive kinetic equations for the chemical relaxation processes. The phase space expression for the rate kernel is reduced to the configuration space result by projecting onto the diffusive eigenfunction of the independent particle diffusive propagator. This reduction shows interplay between the collision dynamics and static structural correlations. The results are compared with earlier theories and possibilities for future developments are discussed.