Classical Time Correlation Function Theory of Proton Transfer Reactions

Abstract

AbstractUsing a correlation function description, we evaluate the rate constant for protonic reactions within the framework of established transition state and diffusion models. We emphasize the dual importance of weak proton‐reservoir coupling and asymptotic time scales for the kinetic isotope effect, the inclusion of internal friction in the rate constant, and specifying the calculated Arrhenius parameters in thermodynamic language. Finally, we link the coupling mechanisms and asymptotic time scales to the interrelated question of the validity of the macroscopic transport law and correlation function description of the rate constant.