Incorporating Electrolyte Correlation Effects into Variational Models of Electrochemical Interfaces.

ABSTRACT: We propose a way for obtaining a classical free energy density functional for electrolytes based on a first-principle many-body partition function. Via a one-loop expansion, we include coulombic correlations beyond the conventional mean-field approximation. To examine electrochemical interfaces, we integrate the electrolyte free energy functional into a hybrid quantum-classical model. This scheme self-consistently couples electronic, ionic, and solvent degrees of freedom and incorporates electrolyte correlation effects. The derived free energy functional causes a correlation-induced enhancement in interfacial counterion density and leads to an overall increase in capacitance. This effect is partially compensated by a reduction of the dielectric permittivity of interfacial water. At larger

SUBMITTER: Bruch N 

PROVIDER: S-EPMC10895655 | biostudies-literature | 2024 Feb

REPOSITORIES: biostudies-literature