Low temperature electron transfer in strongly condensed phase

TL;DR

This paper develops a quantum generalization of the Zusman equations to study low-temperature electron transfer in condensed phases, incorporating quantum fluctuations, and validates the approach with quantum Monte Carlo data.

Contribution

It introduces a novel quantum extension of the Zusman equations for electron transfer, applicable at low temperatures with quantum fluctuations, and provides a comprehensive phase space analysis.

Findings

Derived electron transfer rates including tunneling effects.

Achieved accurate agreement with quantum Monte Carlo simulations.

Extended classical models to quantum regimes successfully.

Abstract

Electron transfer coupled to a collective vibronic degree of freedom is studied in strongly condensed phase and at lower temperatures where quantum fluctuations are essential. Based on an exact representation of the reduced density matrix of the electronic+reaction coordinate compound in terms of path integrals, recent findings on the overdamped limit in quantum dissipative systems are employed. This allows to give for the first time a consistent generalization of the well-known Zusman equations to the quantum domain. Detailed conditions for the range of validity are specified. Using the Wigner transform these results are also extended to the quantum dynamics in full phase space. As an important application electronic transfer rates are derived that comprise adiabatic and nonadiabatic processes in the low temperature regime including nuclear tunneling. Accurate agreement with precise quantum Monte Carlo data is observed.