Classical Approach to Multichromophoric Resonance Energy Transfer

TL;DR

This paper develops a classical electrodynamics-based formulation of multichromophoric resonance energy transfer, accurately predicting enhanced transfer rates and aligning with quantum theory under linear response conditions.

Contribution

It introduces a classical approach to multichromophoric resonance energy transfer that matches quantum results and explains rate enhancements in molecular aggregates.

Findings

Accurately predicts energy transfer rate enhancements in multichromophoric systems.

Shows classical theory aligns with quantum formulation under linear response.

Validates the theory with experimental data on LH II.

Abstract

A classical formulation of the quantum multichromophoric theory of resonance energy transfer is developed on the basis of classical electrodynamics. The theory allows for the identification of a variety of processes of different order-in-the-interactions that contribute to the energy transfer in molecular aggregates with intra-coupling in donors and acceptor chromophores. Enhanced rates in multichromophoric resonance energy transfer are shown to be well described by this theory. Specifically, in a coupling configuration between N_{\mathrm{A}}$ acceptors and $N_{\mathrm{D}}$ donors, the theory correctly predicts an enhancement of the energy transfer rate dependent on the total number of donor-acceptor pairs. As an example, the theory, applied to the transfer rate in LH~II, gives results in excellent agreement with experiment. Finally, it is explicitly shown that as long as linear response theory holds, the classical multichromophoric theory formally coincides with the quantum formulation.