| Autor: |
Bruch, Nils, Binninger, Tobias, Huang, Jun, Eikerling, Michael |
| Rok vydání: |
2024 |
| Předmět: |
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| Druh dokumentu: |
Working Paper |
| Popis: |
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. |
| Databáze: |
arXiv |
| Externí odkaz: |
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