Beyond Born-Oppenheimer Time-Dependent Density Functional Theory
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arXiv
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| Auteurs principaux: | , , |
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| Format: | Preprint |
| Publié: |
2025
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| _version_ | 1866915614776360960 |
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| author | Li, Chen Requist, Ryan Gross, E. K. U. |
| author_facet | Li, Chen Requist, Ryan Gross, E. K. U. |
| contents | We formulate a time-dependent density functional theory for the coupled dynamics of electrons and nuclei that goes beyond the Born-Oppenheimer (BO) approximation. We prove that the time-dependent marginal nuclear probability density $|χ({\bdu R},t)|^2$, the conditional electronic density $n_{\bdu R}(\br,t)$, and the current density $\bm J_{\bdu R}(\br,t)$ are sufficient to uniquely determine the full time-evolving electron-nuclear wave function, and thus the dynamics of all observables. Moreover, we propose a time-dependent Kohn-Sham scheme which reproduces the exact conditional electronic density and current density and the exact N-body nuclear density. The remaining task is to look for functional approximations for the Kohn-Sham exchange-correlation scalar and vector potentials. Using a model driven proton transfer system, we numerically demonstrate that the adiabatic extension of a beyond-BO ground state functional captures the dominant nonadiabatic effects in the regime of slow driving. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2511_09899 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Beyond Born-Oppenheimer Time-Dependent Density Functional Theory Li, Chen Requist, Ryan Gross, E. K. U. Chemical Physics We formulate a time-dependent density functional theory for the coupled dynamics of electrons and nuclei that goes beyond the Born-Oppenheimer (BO) approximation. We prove that the time-dependent marginal nuclear probability density $|χ({\bdu R},t)|^2$, the conditional electronic density $n_{\bdu R}(\br,t)$, and the current density $\bm J_{\bdu R}(\br,t)$ are sufficient to uniquely determine the full time-evolving electron-nuclear wave function, and thus the dynamics of all observables. Moreover, we propose a time-dependent Kohn-Sham scheme which reproduces the exact conditional electronic density and current density and the exact N-body nuclear density. The remaining task is to look for functional approximations for the Kohn-Sham exchange-correlation scalar and vector potentials. Using a model driven proton transfer system, we numerically demonstrate that the adiabatic extension of a beyond-BO ground state functional captures the dominant nonadiabatic effects in the regime of slow driving. |
| title | Beyond Born-Oppenheimer Time-Dependent Density Functional Theory |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2511.09899 |