TY  - JOUR
AU  - Bruch, Nils
AU  - Binninger, Tobias
AU  - Huang, Jun
AU  - Eikerling, Michael
TI  - Incorporating Electrolyte Correlation Effects into Variational Models of Electrochemical Interfaces
JO  - The journal of physical chemistry letters
VL  - 15
IS  - 7
SN  - 1948-7185
CY  - Washington, DC
PB  - ACS
M1  - FZJ-2024-01600
SP  - 2015 - 2022
PY  - 2024
AB  - 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.
LB  - PUB:(DE-HGF)16
C6  - 38349906
UR  - <Go to ISI:>//WOS:001167244700001
DO  - DOI:10.1021/acs.jpclett.3c03295
UR  - https://juser.fz-juelich.de/record/1023017
ER  -