On the Application of Kramers' Theory to Elementary Chemical Reactions

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Abstract
Kramers' diffusion model in the energy controlled low viscosity and the momentum controlled high viscosity range is confronted with reality for elementary unimolecular reactions and radical associations in dense media. Collisional energy transfer appears to be much more complicated than described by the idealized model. On the other hand, there are examples where the Kramers‐Smoluchowski equation well describes the transition to high viscosity behavior. In other cases, solvent shifts of the reaction barriers are pronounced and superimposed on the transport effects described by Kramers' model.