The transition from nonadiabatic to solvent controlled adiabatic electron transfer: Solvent dynamical effects in the inverted regime

• DOI: 10.1063/1.457514
• Publication Date: 2002-07-26T13:19:38Z
• Authors: D. Y. Yang; R. I. Cukier
• Keywords: Reaction coordinate; Hamiltonian (control theory); Conical intersection; Acceptor

We analyze the effect of dynamical solvent effects on rate a nonadiabatic electron transfer (ET) reaction. Starting from Hamiltonian for reaction coordinate motion along potential surfaces donor and acceptor species, bath representing effects, we obtain system four coupled reduced equations elements density matrix donor/acceptor system. In this derivation dynamics are to classical Fokker–Planck operator since assume temperature is high compared with frequencies. At temperatures where nuclear describing transition between can be treated classically show that ET processes may viewed as consecutive scheme constant k=kNA kD/(kD+kNA), steps diffusion kD followed by crossing at point intersection kNA. kNA given an activated expression independent dynamics, e.g., dielectric relaxation time. When must quantum mechanically, favored in inverted regime (where have slopes same sign their point), no longer confined point. approximate above form incorporates width transition. Then kNAdepends dynamics. separation into diffusive appropriate, use basis set expansion method directly solve k. These results formula above.