Investigating the Electrochemical Double Layer with Quantum‐Chemical Simulations and Implicit Solvation Models
- 1Department of Chemistry and Catalysis Research Center TUM School of Natural Sciences Technical University Munich Garching Germany
- 2Atomistic Modeling Center Munich Data Science Institute Garching Germany
Abstract
We assess the dielectrically consistent reference interaction site model (DRISM) as an implicit electrolyte framework for modeling the electrochemical double layer, and compare it with the Poisson–Boltzmann model and explicit molecular dynamics results from the literature. We use the gold–electrolyte interface as the main test case and analyze solvent and ionic density profiles, the differential capacitance, and the solvation contribution to CO adsorption. The results show a strong sensitivity to the Lennard‐Jones parametrization of metal–ion and metal–water interactions. In particular, we find that the default Lorentz–Berthelot mixing rules are inadequate and lead to excessive accumulation at the interface, which results in an increase of the differential capacitance at negative electrode potentials. We demonstrate that introducing pair‐specific metal–ion parameters yields more symmetric charging behavior and provides greater flexibility. Our findings suggest that using pair‐specific parameters, rather than relying on Lorentz–Berthelot mixing rules, improves the accuracy of the model and opens the way for future studies with this improved yet equally performant model.
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BibTeX
@article{mangiameli2026investigating,
title = {{Investigating the Electrochemical Double Layer with Quantum‐Chemical Simulations and Implicit Solvation Models}},
author = {Alessandro Mangiameli and Christopher J. Stein},
journal = {Chemistry (Weinheim an Der Bergstrasse, Germany)},
year = {2026},
month = aug,
doi = {10.1002/chem.71502},
url = {https://doi.org/10.1002/chem.71502},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Investigating the Electrochemical Double Layer with Quantum‐Chemical Simulations and Implicit Solvation Models
AU - Alessandro Mangiameli
AU - Christopher J. Stein
PY - 2026
DA - 2026/08/11
JO - Chemistry (Weinheim an Der Bergstrasse, Germany)
DO - 10.1002/chem.71502
UR - https://doi.org/10.1002/chem.71502
AB - We assess the dielectrically consistent reference interaction site model (DRISM) as an implicit electrolyte framework for modeling the electrochemical double layer, and compare it with the Poisson–Boltzmann model and explicit molecular dynamics results from the literature. We use the gold–electrolyte interface as the main test case and analyze solvent and ionic density profiles, the differential capacitance, and the solvation contribution to CO adsorption. The results show a strong sensitivity to the Lennard‐Jones parametrization of metal–ion and metal–water interactions. In particular, we find that the default Lorentz–Berthelot mixing rules are inadequate and lead to excessive accumulation at the interface, which results in an increase of the differential capacitance at negative electrode potentials. We demonstrate that introducing pair‐specific metal–ion parameters yields more symmetric charging behavior and provides greater flexibility. Our findings suggest that using pair‐specific parameters, rather than relying on Lorentz–Berthelot mixing rules, improves the accuracy of the model and opens the way for future studies with this improved yet equally performant model.
SN - 0947-6539
SN - 1521-3765
ER -