The Phase-Space Way To Electronic Structure Theory and Subsequently Chemical Dynamics
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arXiv
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2025
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| author | Bian, Xuezhi Duston, Titouan Bradbury, Nadine Tao, Zhen Bhati, Mansi Qiu, Tian Wu, Xinchun Wu, Yanze Subotnik, Joseph E. |
| author_facet | Bian, Xuezhi Duston, Titouan Bradbury, Nadine Tao, Zhen Bhati, Mansi Qiu, Tian Wu, Xinchun Wu, Yanze Subotnik, Joseph E. |
| contents | Phase-space electronic structure theory offers up a new and powerful approach for tackling problems with coupled nuclear-electronic dynamics in a fashion that goes beyond Born-Oppenheimer (BO) theory. Whereas BO theory stipulates that we consider electronic states parameterized by nuclear position $X$ only, i.e. molecular orbitals are functions of nuclear positions but not nuclear velocities, phase-space (PS) theory allows for electronic states to be parameterized by both nuclear position X and nuclear momentum $P$. As a result, within a phase-space approach, one can directly recover many new features, including electronic momentum and vibrational circular dichroism spectra. Moreover, phase-space electronic structure theory is exact for the hydrogen atom and, for a set of model problems, the method can even improve upon vibrational energies relative to BO theory. Perhaps most importantly, the phase-space approach offers up a very new perspective on spin physics, stipulating that molecules and materials with degenerate or nearly degenerate ground states (due to spin degeneracy) display broken-symmetry ground states in their phase-space potential energy surfaces. This last feature opens up very new possibilities for exploring spin chemistry (including the Einstein-de Haas effect and chiral induced spin selectivity) within the context of more established electronic structure theory. At the end of the day, in order to tackle electronic dynamical phenomena, especially subtle problems in magnetic chemistry, it will be essential for the electronic structure community to pivot towards diagonalizing $\hat H_{PS}(X, P)$ rather than $\hat H_{BO}(X)$. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2506_15994 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | The Phase-Space Way To Electronic Structure Theory and Subsequently Chemical Dynamics Bian, Xuezhi Duston, Titouan Bradbury, Nadine Tao, Zhen Bhati, Mansi Qiu, Tian Wu, Xinchun Wu, Yanze Subotnik, Joseph E. Chemical Physics Phase-space electronic structure theory offers up a new and powerful approach for tackling problems with coupled nuclear-electronic dynamics in a fashion that goes beyond Born-Oppenheimer (BO) theory. Whereas BO theory stipulates that we consider electronic states parameterized by nuclear position $X$ only, i.e. molecular orbitals are functions of nuclear positions but not nuclear velocities, phase-space (PS) theory allows for electronic states to be parameterized by both nuclear position X and nuclear momentum $P$. As a result, within a phase-space approach, one can directly recover many new features, including electronic momentum and vibrational circular dichroism spectra. Moreover, phase-space electronic structure theory is exact for the hydrogen atom and, for a set of model problems, the method can even improve upon vibrational energies relative to BO theory. Perhaps most importantly, the phase-space approach offers up a very new perspective on spin physics, stipulating that molecules and materials with degenerate or nearly degenerate ground states (due to spin degeneracy) display broken-symmetry ground states in their phase-space potential energy surfaces. This last feature opens up very new possibilities for exploring spin chemistry (including the Einstein-de Haas effect and chiral induced spin selectivity) within the context of more established electronic structure theory. At the end of the day, in order to tackle electronic dynamical phenomena, especially subtle problems in magnetic chemistry, it will be essential for the electronic structure community to pivot towards diagonalizing $\hat H_{PS}(X, P)$ rather than $\hat H_{BO}(X)$. |
| title | The Phase-Space Way To Electronic Structure Theory and Subsequently Chemical Dynamics |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2506.15994 |