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arXiv · 2602.23748

Molecular Electron Transfer in Optical Cavities: From Excitonic to Vibronic Polaritons

Takumi Hidaka·Tomohiro Fukushima·Nguyen Thanh Phuc
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Abstract

Strong coupling between molecular excitations and quantized electromagnetic fields in optical cavities provides a powerful means to control the physical and chemical properties of molecular systems. Here, we study electron transfer (ET) dynamics in cavity-coupled molecules using the numerically exact hierarchical equations of motion (HEOM) method, which captures nonperturbative and non-Markovian effects beyond standard perturbative theories. We identify distinct resonance and collective effects associated with polariton formation and show that the ET rate saturates in the strong-coupling regime, a feature not captured by perturbative approaches. We further extend the cavity-modified ET model by incorporating the nuclear-coordinate dependence of molecular electric dipole moments, which gives rise to a three-body interaction involving molecular electronic and vibrational degrees of freedom and cavity photons. This vibronic polariton formation leads to non-monotonic, oscillatory dependencies of the ET rate on the light-matter coupling strength and cavity frequency, which we attribute to quantum interference among multiple transfer pathways. These findings establish cavity-modified electron transfer as a multichannel quantum process governed by the interplay of electronic, vibrational, and photonic degrees of freedom.

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Takumi Hidaka, Tomohiro Fukushima, Nguyen Thanh Phuc. 2026-02-27. Molecular Electron Transfer in Optical Cavities: From Excitonic to Vibronic Polaritons. https://doi.org/10.1063/5.0331702

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