A Comprehensive Approach to Exciton Delocalization and Energy Transfer.

Abstract

Electrostatic intermolecular interactions lie at the heart of both the Förster model for resonance energy transfer (RET) and the exciton model for energy delocalization. In the Förster theory of RET, the excitation energy incoherently flows from the energy donor to a weakly coupled energy acceptor. The exciton model describes instead the energy delocalization in aggregates of identical (or nearly so) molecules. Here, we introduce a model that brings together molecular aggregates and RET. We will consider a couple of molecules, each described in terms of two diabatic electronic states, coupled to an effective molecular vibration. Electrostatic intermolecular interactions drive energy fluxes between the molecules, that, depending on model parameters, can be described as RET or energy delocalization. At variance with the standard Förster model for RET and of the exciton model for aggregates, our approach applies both in the weak and in the strong coupling regimes and fully accounts for the quantum nature of molecular vibrations in a nonadiabatic approach. Coupling the system to a thermal bath, we follow RET and energy delocalization in real time and simulate time-resolved emission spectra.