Excitation energy transfer between closely spaced multichromophoric systems: Effects of band mixing and intraband relaxation

TL;DR

This paper develops a nonperturbative theoretical framework for excitation energy transfer between closely spaced multichromophoric systems, accounting for band mixing and intraband relaxation effects that challenge traditional F"orster theory.

Contribution

It introduces a nonperturbative method to describe energy transfer involving band mixing and phonon-assisted relaxation, extending beyond F"orster's perturbative approach.

Findings

Conventional F"orster theory fails for closely spaced aggregates due to band overlap.

The nonperturbative approach accurately describes energy transfer in these systems.

Interference effects complicate the experimental determination of transfer rates.

Abstract

We theoretically analyze the excitation energy transfer between two closely spaced linear molecular J-aggregates, whose excited states are Frenkel excitons. The aggregate with the higher (lower) exciton band edge energy is considered as the donor (acceptor). The celebrated theory of F\"orster resonance energy transfer (FRET), which relates the transfer rate to the overlap integral of optical spectra, fails in this situation. We point out that in addition to the well-known fact that the point-dipole approximation breaks down (enabling energy transfer between optically forbidden states), also the perturbative treatment of the electronic interactions between donor and acceptor system, which underlies the F\"orster approach, in general loses its validity due to overlap of the exciton bands. We therefore propose a nonperturbative method, in which donor and acceptor bands are mixed and the energy transfer is described in terms of a phonon-assisted energy relaxation process between the two new (renormalized) bands. The validity of the conventional perturbative approach is investigated by comparing to the nonperturbative one; in general this validity improves for lower temperature and larger distances (weaker interactions) between the aggregates. We also demonstrate that the interference between intraband relaxation and energy transfer renders the proper definition of the transfer rate and its evaluation from experiment a complicated issue, which involves the initial excitation condition.