Phase Space Electronic Structure Theory: From Diatomic Lambda-Doubling to Macroscopic Einstein-de Haas
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| Main Authors: | , , , , , , , |
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| Format: | Preprint |
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2025
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| _version_ | 1866912842457808896 |
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| author | Peng, Linqing Qiu, Tian Bradbury, Nadine Bian, Xuezhi Bhati, Mansi Littlejohn, Robert Kidwell, Nathanael M. Subotnik, Joseph E. |
| author_facet | Peng, Linqing Qiu, Tian Bradbury, Nadine Bian, Xuezhi Bhati, Mansi Littlejohn, Robert Kidwell, Nathanael M. Subotnik, Joseph E. |
| contents | $Λ$-doubling of diatomic molecules is a subtle microscopic phenomenon that has long attracted the attention of experimental groups, insofar as rotation of molecular $\textit{nuclei}$ induces small energetic changes in the (degenerate) $\textit{electronic}$ state. A direct description of such a phenomenon clearly requires going beyond the Born-Oppenheimer approximation. Here we show that a phase space theory previously developed to capture electronic momentum and model vibrational circular dichroism -- and which we have postulated should also describe the Einstein-de Haas effect, a macroscopic manifestation of angular momentum conservation -- is also able to recover the $Λ$-doubling energy splitting (or $Λ$-splitting) of the NO molecule nearly quantitatively. The key observation is that, by parameterizing the electronic Hamiltonian in terms of both nuclear position ($\mathbf{X}$) and nuclear momentum ($\mathbf{P}$), a phase space method yields potential energy surfaces that explicitly include the electron-rotation coupling and correctly conserve angular momentum (which we show is essential to capture $Λ-$doubling). The data presented in this manuscript offers another small glimpse into the rich physics that one can learn from investigating phase space potential energy surfaces $E_{PS}(\mathbf{X},\mathbf{P})$ as a function of both nuclear position and momentum, all at a computational cost comparable to standard Born-Oppenheimer electronic structure calculations. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2512_13448 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Phase Space Electronic Structure Theory: From Diatomic Lambda-Doubling to Macroscopic Einstein-de Haas Peng, Linqing Qiu, Tian Bradbury, Nadine Bian, Xuezhi Bhati, Mansi Littlejohn, Robert Kidwell, Nathanael M. Subotnik, Joseph E. Chemical Physics Atomic Physics Quantum Physics $Λ$-doubling of diatomic molecules is a subtle microscopic phenomenon that has long attracted the attention of experimental groups, insofar as rotation of molecular $\textit{nuclei}$ induces small energetic changes in the (degenerate) $\textit{electronic}$ state. A direct description of such a phenomenon clearly requires going beyond the Born-Oppenheimer approximation. Here we show that a phase space theory previously developed to capture electronic momentum and model vibrational circular dichroism -- and which we have postulated should also describe the Einstein-de Haas effect, a macroscopic manifestation of angular momentum conservation -- is also able to recover the $Λ$-doubling energy splitting (or $Λ$-splitting) of the NO molecule nearly quantitatively. The key observation is that, by parameterizing the electronic Hamiltonian in terms of both nuclear position ($\mathbf{X}$) and nuclear momentum ($\mathbf{P}$), a phase space method yields potential energy surfaces that explicitly include the electron-rotation coupling and correctly conserve angular momentum (which we show is essential to capture $Λ-$doubling). The data presented in this manuscript offers another small glimpse into the rich physics that one can learn from investigating phase space potential energy surfaces $E_{PS}(\mathbf{X},\mathbf{P})$ as a function of both nuclear position and momentum, all at a computational cost comparable to standard Born-Oppenheimer electronic structure calculations. |
| title | Phase Space Electronic Structure Theory: From Diatomic Lambda-Doubling to Macroscopic Einstein-de Haas |
| topic | Chemical Physics Atomic Physics Quantum Physics |
| url | https://arxiv.org/abs/2512.13448 |