Phonon-mediated path-interference in electronic energy transfer

Abstract

We present a formalism to quantify the contribution of path-interference in phonon-mediated electronic energy transfer. The transfer rate between two molecules is computed by considering the quantum mechanical amplitudes associated with pathways connecting the initial and final sites. This includes contributions from classical pathways, but also terms arising from interference of different pathways. We treat the vibrational modes coupled to the molecules as a non-Markovian harmonic oscillator bath, and investigate the correction to transfer rates due to the lowest-order interference contribution. We show that depending on the structure of the harmonic bath, the correction due to path-interference may have a dominant vibrational or electronic character, and can make a notable contribution to the transfer rate in the steady state. © 2012 American Institute of Physics.