2024/11/25 by Nils Bruch, Bruch, Nils, Tobias Binninger +5 · 2 citations
Chemistry · #Chemical Physics (physics.chem-ph) #Electrostatics and Colloid Interactions #FOS: Physical sciences #Statistical Mechanics (cond-mat.stat-mech)
paper · pdf · doi:10.48550/arxiv.2411.16521
openalex publication_date 2024/11/25 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
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.