Coherent quantum dynamics in donor-bridge-acceptor systems: Beyond the hopping and super-exchange mechanisms

Abstract: The population transfer dynamics of model donor-bridge-acceptor systems is studied by comparing a recently developed polaron-transformed quantum master equation (PQME) with the well-known Redfield and Forster theories of quantum transport. We show that the PQME approach reduces to these two theories in their respective limits of validity and naturally interpolates between them as a function of the system-bath coupling strength. By exploring the parameter space of our model problem, we identify novel regimes of transport dynamics in bridged systems like those encountered in biological and organic energy transfer problems. Furthermore, we demonstrate that three-level systems like the ones studied herein represent ideal minimal models for the identification of quantum coherent transport as embodied in super-exchange phenomena that cannot be captured by Forster-like hopping approaches.