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| Autori principali: | , , |
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| Natura: | Preprint |
| Pubblicazione: |
2025
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| Accesso online: | https://arxiv.org/abs/2510.11810 |
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| _version_ | 1866917010914410496 |
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| author | Cofer-Shabica, D. Vale DeRosa, Jennifer R. Subotnik, Joseph E. |
| author_facet | Cofer-Shabica, D. Vale DeRosa, Jennifer R. Subotnik, Joseph E. |
| contents | Marcus theory is the workhorse of theoretical chemistry for predicting the rates of charge and energy transfer. Marcus theory overwhelmingly agrees with experiment -- both in terms of electron transfer and triplet energy transfer -- for the famous set of naphthalene-bridge-biphenyl and naphthalene-bridge-benzophenone systems studied by Piotrowiak, Miller, and Closs. That being said, the agreement is not perfect, and in this manuscript, we revisit one key point of disagreement: the molecule C-13-ae ([3,equatorial]-naphthalene-cyclohexane-[1,axial]-benzophenone). To better understand the theory-experiment disagreement, we introduce and employ a novel scheme to sample the seam between two diabatic electronic states (E-SHAKE) through which we reveal the breakdown of the Condon approximation and the presence of a conical intersection for the C-13-ae molecule; we also predict an isotopic effect on the rate of triplet-triplet energy transfer. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2510_11810 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Marcus Theory and The Condon Approximation Revisited I: E-SHAKE and Seam Sampling Cofer-Shabica, D. Vale DeRosa, Jennifer R. Subotnik, Joseph E. Chemical Physics Marcus theory is the workhorse of theoretical chemistry for predicting the rates of charge and energy transfer. Marcus theory overwhelmingly agrees with experiment -- both in terms of electron transfer and triplet energy transfer -- for the famous set of naphthalene-bridge-biphenyl and naphthalene-bridge-benzophenone systems studied by Piotrowiak, Miller, and Closs. That being said, the agreement is not perfect, and in this manuscript, we revisit one key point of disagreement: the molecule C-13-ae ([3,equatorial]-naphthalene-cyclohexane-[1,axial]-benzophenone). To better understand the theory-experiment disagreement, we introduce and employ a novel scheme to sample the seam between two diabatic electronic states (E-SHAKE) through which we reveal the breakdown of the Condon approximation and the presence of a conical intersection for the C-13-ae molecule; we also predict an isotopic effect on the rate of triplet-triplet energy transfer. |
| title | Marcus Theory and The Condon Approximation Revisited I: E-SHAKE and Seam Sampling |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2510.11810 |