Environment-modified three-body energy transfer

TL;DR

This paper introduces a perturbation theory-based method to efficiently calculate three-body resonance energy transfer rates in environments, demonstrating how a third molecule near a dielectric interface can enhance or suppress transfer rates.

Contribution

The authors develop a canonical perturbation theory approach to simplify the calculation of three-body energy transfer rates in complex environments, providing a practical formula and demonstrating its application.

Findings

The method reduces computational complexity of rate calculations.

The third molecule can significantly modify energy transfer rates.

Environmental factors like dielectric interfaces influence transfer dynamics.

Abstract

Resonant energy transfer from a donor to an acceptor is one of the most basic interactions between atomic and molecular systems. In real-life situations, the donor and acceptor are not isolated but in fact coupled to their environment and to other atoms and molecules. The presence of a third body can modify the rate of energy transfer between donor and acceptor in distinctive and intricate ways, especially when the three-site system is itself interacting with a larger macroscopic background such as a solvent. The rate can be calculated perturbatively, which ordinarily requires the summation of very large numbers of Feynman-like diagrams. Here we demonstrate a method based on canonical perturbation theory that allows us to reduce the computational effort required, and use this technique to derive a formula for the rate of three-body resonance energy transfer in a background environment. As a proof-of-principle, we apply this to the situation of a dimer positioned near a dielectric interface, with a distant third molecule controlling the rate, finding both enhancement or suppression of the rate depending on system parameters.