Electron Transfer, Diabatic Couplings and Vibronic Energy Gaps in a Phase Space Electronic Structure Framework
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arXiv
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| Format: | Preprint |
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2026
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| _version_ | 1866908935680688128 |
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| author | Zaidi, Zain Bian, Xuezhi Subotnik, Joseph E. |
| author_facet | Zaidi, Zain Bian, Xuezhi Subotnik, Joseph E. |
| contents | We investigate the well-known Shin-Metiu model for an electronic crossing, using both a standard Born-Huang (BH) framework and a novel phase space (PS) electronic Hamiltonian framework. We show that as long as we are not in the strongly nonadiabatic region, a phase space framework can obtain a relative error in vibrational energy gap and other vibronic matrix elements that are consistently one order of magnitude smaller than what is found within a BH framework. In line with recent results showing that dynamics on one phase space surface can outperform dynamics on one Born-Oppenheimer surface, our results indicate that the same advantages should largely hold for curve crossings and dynamics on two or a handful of electronic surfaces, from which several implications can be surmised as far as the possibility of spin-dependent electron transfer dynamics. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2601_16209 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Electron Transfer, Diabatic Couplings and Vibronic Energy Gaps in a Phase Space Electronic Structure Framework Zaidi, Zain Bian, Xuezhi Subotnik, Joseph E. Chemical Physics We investigate the well-known Shin-Metiu model for an electronic crossing, using both a standard Born-Huang (BH) framework and a novel phase space (PS) electronic Hamiltonian framework. We show that as long as we are not in the strongly nonadiabatic region, a phase space framework can obtain a relative error in vibrational energy gap and other vibronic matrix elements that are consistently one order of magnitude smaller than what is found within a BH framework. In line with recent results showing that dynamics on one phase space surface can outperform dynamics on one Born-Oppenheimer surface, our results indicate that the same advantages should largely hold for curve crossings and dynamics on two or a handful of electronic surfaces, from which several implications can be surmised as far as the possibility of spin-dependent electron transfer dynamics. |
| title | Electron Transfer, Diabatic Couplings and Vibronic Energy Gaps in a Phase Space Electronic Structure Framework |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2601.16209 |