Wide-Dynamic-Range Control of Quantum-Electrodynamic Electron Transfer Reactions in the Weak Coupling Regime

Abstract

Catalyzing reactions effectively by vacuum fluctuations of electromagnetic fields is a significant challenge within the realm of chemistry. Different from most studies based on vibrational strong coupling, we introduce an innovative catalytic mechanism driven by weakly coupled polaritonic fields. Through the amalgamation of macroscopic quantum electrodynamics (QED) principles with Marcus electron transfer (ET) theory, our results reveal that ET reaction rates can be precisely modulated across a wide dynamic range by controlling the size and structure of nanocavities. Comparing to QED-driven radiative ET rates in free space, plasmonic cavities induce substantial rate enhancements spanning from orders of magnitude ranging from 10^3-fold to 10^1-fold. By contrast, Fabry-Perot cavities engender rate suppression spanning from 10^{-2}-fold to 10^{-1}-fold. This work overcomes the necessity of using strong light-matter interactions in QED chemistry, opening up a new era of manipulating QED-based chemical reactions in a wide dynamic range