Enhanced photoisomerization with hybrid metallodielectric cavities based on mode interference.

This article investigates the control of photoisomerization reactions at the single-molecule level using hybrid metallodielectric cavities, which combine photonic and plasmonic modes. It demonstrates that interference between these two modes enables an energy-selective Purcell effect—an enhancement of spontaneous emission rates—that selectively accelerates relaxation to a desired molecular geometry, thereby increasing the yield of photoisomerization reactions. Using the asymmetric proton transfer in (Z)-3-aminoacrylaldehyde as a case study, the authors show that optimized hybrid cavities outperform single-mode plasmonic cavities by achieving higher population transfer to the target isomeric state under realistic parameters. The study employs electronic-structure calculations and rate equations incorporating cavity effects, highlighting the robustness of the hybrid cavity's energy selectivity and its potential for advancing cavity-induced photochemical control.