Cavity-Free Quantum-Electrodynamic Electron Transfer Reactions

Richard Feynman stated that ‘The theory behind chemistry is quantum electrodynamics’. However, harnessing quantum-electrodynamic (QED) effects to modify chemical reactions is a grand challenge and currently has only been reported in experiments using cavities due to the limitation of strong light-matter coupling. In this article, we demonstrate that QED effects can significantly enhance the rate of electron transfer (ET) reactions by several orders of magnitude in the absence of cavities, which is implicitly supported by experimental reports. To understand how cavity-free QED effects are involved in ET reactions, we incorporate the effect of infinite one-photon states into Marcus theory, derive an explicit expression for the rate of radiative ET, and develop the concept of “electron transfer overlap”. Moreover, QED effects may lead to a barrier-free ET reaction in which the rate is dependent on the energy-gap power law. This study thus provides new insights into fundamental chemical principles, with promising prospects for QED-based chemical reactions.