中央研究院 原子與分子科學研究所

Catalyzing reactions effectively by vacuum fluctuations of electromagnetic fields is a significant challenge within the realm of chemistry. As opposed to 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, we predict that ET reaction rates can be precisely modulated across a wide dynamic range by controlling the size and structure of nanocavities. Compared to QED-driven radiative ET rates in free space, plasmonic cavities induce substantial rate enhancements spanning the range from 10³- to 10-fold. By contrast, Fabry–Perot cavities engender rate suppression spanning the range from 10^–2- 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.

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