Cavity-modified exciton-exciton annihilation in disordered molecular systems

TL;DR

This study uses numerical simulations to clarify how strong light-matter coupling influences exciton-exciton annihilation in disordered molecular systems, revealing conditions that either enhance or suppress EEA rates.

Contribution

It demonstrates how strong coupling can modify EEA rates by affecting exciton delocalization and disorder, resolving previous experimental contradictions.

Findings

Strong coupling can increase EEA rate by delocalizing excitons in disordered systems.

High exciton mobility reduces the impact of strong coupling on EEA.

Weak coupling suppresses EEA due to photon leakage decay channels.

Abstract

Recent experiments have shown contradictory effects of strong light-matter coupling on exciton-exciton annihilation (EEA) in organic molecular systems. In this work, we perform numerical simulations of polariton dynamics and reveal the role of strong coupling in changing the EEA rate. The results of our simulations suggest that strong coupling allows to partially overcome disorder in systems with poor exciton mobility via delocalisation of excitons owing to the interaction with the common cavity mode. This leads to an enhanced connectivity between excitons and, consequently, to an increase in the EEA rate. Conversely, in systems with high exciton mobility, in which disorder has a much smaller effect on excitation energy transfer, excitons can interact strongly even without coupling to the cavity photons at the exciton densities at which EEA typically occurs. In this case, the EEA rate can be even lower than in bare molecules due to the existence of a competing decay channel associated with photon leakage through the cavity mirrors. We also find that in the weak coupling regime, the EEA rate appears to be suppressed due to this decay channel regardless of the exciton transport properties. Our simulations resolve the experimental controversy on the effect of strong coupling on EEA and provide guidance for minimising the EEA rate towards a more feasible realisation of Bose-Einstein condensation of polaritons.