Molecular Electron Transfer in Optical Cavities: From Excitonic to Vibronic Polaritons
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arXiv
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| Format: | Preprint |
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2026
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| _version_ | 1866912930087305216 |
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| author | Hidaka, Takumi Fukushima, Tomohiro Phuc, Nguyen Thanh |
| author_facet | Hidaka, Takumi Fukushima, Tomohiro Phuc, Nguyen Thanh |
| contents | 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. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2602_23748 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Molecular Electron Transfer in Optical Cavities: From Excitonic to Vibronic Polaritons Hidaka, Takumi Fukushima, Tomohiro Phuc, Nguyen Thanh Chemical Physics Mesoscale and Nanoscale Physics Quantum Physics 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. |
| title | Molecular Electron Transfer in Optical Cavities: From Excitonic to Vibronic Polaritons |
| topic | Chemical Physics Mesoscale and Nanoscale Physics Quantum Physics |
| url | https://arxiv.org/abs/2602.23748 |