Reactive modes in condensed phase reactions

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Abstract
The rate constantk for condensed phase chemical reactions is found when a saddle point normal modeanalysis holds and when the dynamic solvent forces are of the generalized Langevin type. If the reactive and nonreactive modes are uncoupled, the deviation of k from its transition state value k tst is governed by the nonadiabaticfriction on the reactive mode. In the more typical case where the modes are coupled k/k tst is governed by an effective nonadiabatic reactive mode friction which completely accounts for intramode coupling. Some simple illustrations of mode coupling effects on k are given.