Multidimensional tunnelling of molecules aligned by strong electric fields
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arXiv
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| Format: | Preprint |
| Publié: |
2025
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| _version_ | 1866915647091376128 |
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| author | Geuther, J. Amira Fiechter, Marit R. Richardson, Jeremy O. |
| author_facet | Geuther, J. Amira Fiechter, Marit R. Richardson, Jeremy O. |
| contents | Strong electric fields can be used to align molecules. However, a non-polar molecule such as H$_2$ has no preference for its orientation. There are thus two equivalent configurations with equal energy separated by a potential-energy barrier. Quantum mechanically, the molecule can tunnel between these configurations resulting in a tunnelling splitting, which in the case of H$_2$, is the same as the ortho--para splitting. In this work, we generalize semiclassical instanton theory to calculate the energy splitting of molecules in electric fields in full dimensionality. This goes beyond a perturbative treatment of the field and takes into account changes in molecular geometry during the tunnelling process which influence its electrical properties and can have a significant impact on the result. We first study the case of H$_2$ in a static electric field and then show how it can be applied to larger polar molecules subjected to oscillating electric fields, where we find that even large-amplitude heavy-atom tunnelling can lead to observable splittings. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2512_01714 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Multidimensional tunnelling of molecules aligned by strong electric fields Geuther, J. Amira Fiechter, Marit R. Richardson, Jeremy O. Chemical Physics Strong electric fields can be used to align molecules. However, a non-polar molecule such as H$_2$ has no preference for its orientation. There are thus two equivalent configurations with equal energy separated by a potential-energy barrier. Quantum mechanically, the molecule can tunnel between these configurations resulting in a tunnelling splitting, which in the case of H$_2$, is the same as the ortho--para splitting. In this work, we generalize semiclassical instanton theory to calculate the energy splitting of molecules in electric fields in full dimensionality. This goes beyond a perturbative treatment of the field and takes into account changes in molecular geometry during the tunnelling process which influence its electrical properties and can have a significant impact on the result. We first study the case of H$_2$ in a static electric field and then show how it can be applied to larger polar molecules subjected to oscillating electric fields, where we find that even large-amplitude heavy-atom tunnelling can lead to observable splittings. |
| title | Multidimensional tunnelling of molecules aligned by strong electric fields |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2512.01714 |