Enhanced photoisomerization with hybrid metallodielectric cavities based on mode interference

TL;DR

This paper demonstrates that hybrid metallodielectric cavities, supporting both photonic and plasmonic modes, can enhance photoisomerization reactions by selectively increasing the yield through interference effects.

Contribution

It introduces the concept of using hybrid cavities with mode interference to control and improve photoisomerization efficiency, a novel approach compared to single-mode cavities.

Findings

Hybrid cavities enable energy-selective Purcell effects.

Interference between modes enhances specific molecular relaxation pathways.

Results are robust across realistic cavity parameters.

Abstract

The ability to control chemical reactions by coupling organic molecules to confined light in a cavity has recently attracted much attention. While most previous studies have focused on single-mode photonic or plasmonic cavities, here we investigate the effect of hybrid metallodielectric cavities on photoisomerization reactions. Hybrid cavities, which support both photonic and plasmonic modes, offer unique opportunities that arise from the interplay between these two distinct types of modes. Specifically, we demonstrate that interference in the spectral density due to a narrow photonic mode and a broad plasmonic mode that are coupled to each other enables hybrid cavities to provide an energy-selective Purcell effect. This effect enhances electronic relaxation only to the desired molecular geometry, providing the ability to increase the yield of photoisomerization reactions. As a test case, we study the asymmetric proton transfer reaction in the electronic excited state of 3-aminoacrolein. Our results, which are robust for a range of realistic cavity parameters, highlight the advantages of hybrid cavities in cavity-induced photochemical processes.