Semiclassical Description of Electronic Excitation Population Transfer in a Model Photosynthetic System

Abstract

Recently, Fleming’s group observed direct evidence that the electronic excitation energy (and population) transfers coherently rather than through incoherent hopping motions in the Fenna−Mathews−Olson pigment−protein complex. Ishizaki and Fleming further developed a hierarchy equation approach to describe this excitation population transfer dynamics in a model photosynthetic system. Here, we treat this same model system via the linearized approximation to the semiclassical (SC) initial value representation (IVR) for time correlation functions, in combination with the Meyer−Miller−Stock−Thoss model for the electronic degrees of freedom. Our approach is able to describe the long-lived quantum coherent dynamics, in excellent agreement with Ishizaki−Fleming’s results. Moreover, the advantage of the linearlized SC-IVR approach is that it can be applied to any molecular model for which classical MD simulations are feasible, all the way up to a full all-atom MD simulation, while at the same time treating the electronic and nuclear dynamics in a consistent fashion.