Journal Article

FZJ-2024-01600

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Incorporating Electrolyte Correlation Effects into Variational Models of Electrochemical Interfaces

Bruch, N.FZJ* ; Binninger, T.FZJ* ; Huang, J.FZJ* ; Eikerling, M. (Corresponding author)FZJ*

2024
ACS Washington, DC

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Please use a persistent id in citations: doi:10.1021/acs.jpclett.3c03295  doi:10.34734/FZJ-2024-01600

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 surface charge densities, ion crowding at the interface stifles these correlation effects. While scientifically intriguing already at planar interfaces, we anticipate these correlation effects to play an essential role for electrolytes in nanoconfinement.

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Contributing Institute(s):

1. IEK-13 (IEK-13)

Research Program(s):

1. 1212 - Materials and Interfaces (POF4-121) (POF4-121)

Appears in the scientific report 2024

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Database coverage:
; ; ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; Essential Science Indicators ; IF >= 5 ; JCR ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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