Resolving the Marcus-Rehm-Weller Paradox in Electron Transfer
Fuente:
arXiv
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| Autor principal: | |
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| Formato: | Preprint |
| Publicado: |
2025
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| _version_ | 1866910144967737344 |
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| author | Abraham, Ethan |
| author_facet | Abraham, Ethan |
| contents | Marcus theory famously predicts that electron-transfer rates decrease once the thermodynamic driving force exceeds the reorganization energy. Yet many systems instead exhibit Rehm-Weller kinetics, in which the rate saturates rather than decreases. Here we show that these apparently contradictory phenomenologies emerge as opposite physical limits of the same two-level quantum Hamiltonian. In the normal region, the model recovers both Marcus and Rehm-Weller behavior. In the inverted region, however, it predicts Marcus's decreasing rate in the nonadiabatic limit but Rehm-Weller saturation in the adiabatic limit. Using physically realistic reorganization energies and electronic coupling values, we show that Rehm-Weller's data can be quantitatively reproduced within a microscopic quantum model without invoking diffusion limitations or phenomenological corrections. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2511_01909 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Resolving the Marcus-Rehm-Weller Paradox in Electron Transfer Abraham, Ethan Chemical Physics Mesoscale and Nanoscale Physics Materials Science Quantum Physics Marcus theory famously predicts that electron-transfer rates decrease once the thermodynamic driving force exceeds the reorganization energy. Yet many systems instead exhibit Rehm-Weller kinetics, in which the rate saturates rather than decreases. Here we show that these apparently contradictory phenomenologies emerge as opposite physical limits of the same two-level quantum Hamiltonian. In the normal region, the model recovers both Marcus and Rehm-Weller behavior. In the inverted region, however, it predicts Marcus's decreasing rate in the nonadiabatic limit but Rehm-Weller saturation in the adiabatic limit. Using physically realistic reorganization energies and electronic coupling values, we show that Rehm-Weller's data can be quantitatively reproduced within a microscopic quantum model without invoking diffusion limitations or phenomenological corrections. |
| title | Resolving the Marcus-Rehm-Weller Paradox in Electron Transfer |
| topic | Chemical Physics Mesoscale and Nanoscale Physics Materials Science Quantum Physics |
| url | https://arxiv.org/abs/2511.01909 |