Self‐consistent hybrid approach for simulating electron transfer reactions in condensed phases

Abstract

AbstractThe recently proposed self‐consistent hybrid method is presented as a numerical tool for simulating quantum dynamics in complex systems. This method is based on an iterative convergence procedure for a dynamical hybrid approach. In this approach the overall system is partitioned into a core and a reservoir. The former is treated via a numerically exact quantum mechanical method, and the latter is treated via a more approximate method. Self‐consistent iterations are then carried out, with the number of core degrees of freedom and other variational parameters increased systematically to achieve numerical convergence for the overall quantum dynamics. The details of treating the core and the reservoir, as well as the convergence procedure, are discussed for several examples of electron transfer reactions in condensed phases. It is shown that the self‐consistent hybrid method provides an accurate and practical way of simulating quantum dissipative dynamics in a wide range of physical regimes.