Generalized energy gap law: An open system dynamics approach to non-adiabatic phenomena in molecules
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arXiv
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| Main Authors: | , , , , , , |
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| Format: | Preprint |
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2024
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| _version_ | 1866910446766784512 |
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| author | Bassler, N. S. Reitz, M. Holzinger, R. Vibók, A. Halász, G. J. Gurlek, B. Genes, C. |
| author_facet | Bassler, N. S. Reitz, M. Holzinger, R. Vibók, A. Halász, G. J. Gurlek, B. Genes, C. |
| contents | Non-adiabatic molecular phenomena, arising from the breakdown of the Born-Oppenheimer approximation, govern the fate of virtually all photo-physical and photochemical processes and limit the quantum efficiency of molecules and other solid-state embedded quantum emitters. A simple and elegant description, the energy gap law, was derived five decades ago, predicting that the non-adiabatic coupling between the excited and ground potential landscapes lead to non-radiative decay with a quasi-exponential dependence on the energy gap. We revisit and extend this theory to account for crucial aspects such as vibrational relaxation, dephasing, and radiative loss. We find a closed analytical solution with general validity which indicates a direct proportionality of the non-radiative rate with the vibrational relaxation rate at low temperatures, and with the dephasing rate of the electronic transition at high temperatures. Our work establishes a connection between nanoscale quantum optics, open quantum system dynamics and non-adiabatic molecular physics. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2405_08718 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Generalized energy gap law: An open system dynamics approach to non-adiabatic phenomena in molecules Bassler, N. S. Reitz, M. Holzinger, R. Vibók, A. Halász, G. J. Gurlek, B. Genes, C. Quantum Physics Mesoscale and Nanoscale Physics Non-adiabatic molecular phenomena, arising from the breakdown of the Born-Oppenheimer approximation, govern the fate of virtually all photo-physical and photochemical processes and limit the quantum efficiency of molecules and other solid-state embedded quantum emitters. A simple and elegant description, the energy gap law, was derived five decades ago, predicting that the non-adiabatic coupling between the excited and ground potential landscapes lead to non-radiative decay with a quasi-exponential dependence on the energy gap. We revisit and extend this theory to account for crucial aspects such as vibrational relaxation, dephasing, and radiative loss. We find a closed analytical solution with general validity which indicates a direct proportionality of the non-radiative rate with the vibrational relaxation rate at low temperatures, and with the dephasing rate of the electronic transition at high temperatures. Our work establishes a connection between nanoscale quantum optics, open quantum system dynamics and non-adiabatic molecular physics. |
| title | Generalized energy gap law: An open system dynamics approach to non-adiabatic phenomena in molecules |
| topic | Quantum Physics Mesoscale and Nanoscale Physics |
| url | https://arxiv.org/abs/2405.08718 |