Variational functional theory for coulombic correlations in the electric double layer
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arXiv
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| Main Authors: | , , , |
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| Format: | Preprint |
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2024
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| _version_ | 1866911448843681792 |
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| author | Bruch, Nils Binninger, Tobias Huang, Jun Eikerling, Michael |
| author_facet | Bruch, Nils Binninger, Tobias Huang, Jun Eikerling, Michael |
| contents | A classical coulombic correlation functional in one-loop (1L) and local-density-approximation (LDA) is derived for electrolyte solutions, starting from a first-principles many-body partition function. The 1L-LDA functional captures correlations between electrolyte ions and solvent dipoles, such as screening and solvation, that are ignored by conventional mean-field theories. This 1L-LDA functional introduces two parameters that can be tuned to the experimental dielectric permittivity and activity coefficients in the bulk electrolyte solution. The capabilities of the 1L-LDA functional for the description of metal-electrolyte interfaces are demonstrated by embedding the functional into a combined quantum-classical model. Here, the 1L-LDA functional leads to a more pronounced double-peak structure of the interfacial capacitance with higher peaks and shorter peak-to-peak distance, significantly improving the agreement with experimental data and showing that electrolyte correlation effects exert a vital impact on the capacitive response. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2411_16521 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Variational functional theory for coulombic correlations in the electric double layer Bruch, Nils Binninger, Tobias Huang, Jun Eikerling, Michael Chemical Physics Statistical Mechanics A classical coulombic correlation functional in one-loop (1L) and local-density-approximation (LDA) is derived for electrolyte solutions, starting from a first-principles many-body partition function. The 1L-LDA functional captures correlations between electrolyte ions and solvent dipoles, such as screening and solvation, that are ignored by conventional mean-field theories. This 1L-LDA functional introduces two parameters that can be tuned to the experimental dielectric permittivity and activity coefficients in the bulk electrolyte solution. The capabilities of the 1L-LDA functional for the description of metal-electrolyte interfaces are demonstrated by embedding the functional into a combined quantum-classical model. Here, the 1L-LDA functional leads to a more pronounced double-peak structure of the interfacial capacitance with higher peaks and shorter peak-to-peak distance, significantly improving the agreement with experimental data and showing that electrolyte correlation effects exert a vital impact on the capacitive response. |
| title | Variational functional theory for coulombic correlations in the electric double layer |
| topic | Chemical Physics Statistical Mechanics |
| url | https://arxiv.org/abs/2411.16521 |