Excitation Energy Transfer Efficiency in Fluctuating Environments: Role of Quantum Coherence in the Presence of Memory Effects.

Abstract

Several recent studies have interrogated the role of quantum coherence in affecting the transfer efficiency of an optical excitation to the designated "trap" state where the energy can be used for subsequent reactions, as in photosynthesis. However, these studies invoke a Markovian approximation for the time correlation function describing the environment-induced stochastic fluctuations. Here, we employ Kubo's quantum stochastic Liouville equation (QSLE) to include memory effects. We extend the existing QSLE scheme to introduce decay of a newly created excitation due to radiative and nonradiative channels and also by desired trapping toward the targeted chromophore. We show that the theoretical formalism based on the QSLE correctly reproduces the rate equation description in the Markovian limit, with the rate constants determined by an appropriate quantum limiting procedure. We find that under certain conditions, the efficiency of excitation transfer to the trap gains from the combined presence of quantum coherence and temporally correlated stochastic fluctuations. We work out different limiting situations in order to discover and quantify the optimum conditions for the energy transfer to the trapped state. We find that maximum energy transfer efficiency is achieved in the intermediate limit between coherent and incoherent transport.