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| Main Authors: | , , , , |
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| Format: | Preprint |
| Published: |
2025
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| Subjects: | |
| Online Access: | https://arxiv.org/abs/2505.11101 |
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| _version_ | 1866918022193610752 |
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| author | Labavić, Darka Brünig, Florian N. Netz, Roland R. Bocquet, Marie-Laure Berthoumieux, Hélène |
| author_facet | Labavić, Darka Brünig, Florian N. Netz, Roland R. Bocquet, Marie-Laure Berthoumieux, Hélène |
| contents | The nonlocal dielectric properties of liquid water are studied in the context of {\it ab initio} molecular dynamics simulations based on density functional theory. We calculate the dielectric response from the charge structure factor of the liquid using the fluctuation-dissipation theorem. We show that the dielectric response function of {\it ab initio} simulations differs significantly from that of classical force-fields, both qualitatively and quantitatively. In particular, it exhibits a larger amplitude and a wider range of responding wave numbers. We suggest that the difference is due to the localisation of the electronic charge density inherent in classical force files and Wannier post-treatment of DFT densities. The localised charge models do not reproduce the shape of the response function even for $q$ corresponding to intermolecular distances, and could lead to a significant underestimation of the dielectric response of the liquid by a factor of 10. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2505_11101 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Nonlocal dielectric properties of water: the role of electronic delocalisation Labavić, Darka Brünig, Florian N. Netz, Roland R. Bocquet, Marie-Laure Berthoumieux, Hélène Chemical Physics The nonlocal dielectric properties of liquid water are studied in the context of {\it ab initio} molecular dynamics simulations based on density functional theory. We calculate the dielectric response from the charge structure factor of the liquid using the fluctuation-dissipation theorem. We show that the dielectric response function of {\it ab initio} simulations differs significantly from that of classical force-fields, both qualitatively and quantitatively. In particular, it exhibits a larger amplitude and a wider range of responding wave numbers. We suggest that the difference is due to the localisation of the electronic charge density inherent in classical force files and Wannier post-treatment of DFT densities. The localised charge models do not reproduce the shape of the response function even for $q$ corresponding to intermolecular distances, and could lead to a significant underestimation of the dielectric response of the liquid by a factor of 10. |
| title | Nonlocal dielectric properties of water: the role of electronic delocalisation |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2505.11101 |