A dynamical approach to electron transfer reactions

Abstract

A time-dependent approach to molecular dynamics involving both electrons and nuclei is formulated to study the interaction between electronic structure and nuclear geometry during electron transfer processes. The formulation uses the time-dependent variational principle to obtain a Hamiltonian system of first-order ordinary differential equations for wave function parameters from the quantum mechanical Schrödinger equation. We apply the formulation to a two-level model. In this first application, the nuclei are treated classically. The electron transfer process in both the “normal” and the “abnormal” case is studied and discussed. The role of the nuclear motion in the electron transfer process is clearly exhibited in both two and three moiety systems. For small coupling the difference in evolution between the dynamics using adiabatic and diabatic basis states shows the importance of nuclear motion in the process. Then various aspects of applications to realistic systems are discussed, and the techniques to treat those applications are outlined.