Systematic Investigation of Classical Molecular Dynamics Models for Ionic Liquid‐Based Electrolytes at Electrode Interfaces
Abstract
Molecular dynamics (MD) simulations are widely used to investigate ionic liquid (IL) electrolytes and their interfaces at electrified electrodes. However, the predicted interfacial nanostructure and chemistry of electrolytes are strongly influenced by methodological choices, including electrode models and force-field treatments, whose relative performance remains insufficiently understood. Here, we systematically evaluate two electrode modelling approaches: the constant charge model (CCM) and the constant potential model (CPM), together with the role of force field polarisability, for studying interfaces of IL-based electrolytes, including neat ILs, salt-containing ILs, and hybrid systems with cosolvents or mixed cations. The aim is to assess how effective these approaches capture potential-dependent interfacial structure and chemistry relevant to battery performance. For neat and salt-containing ILs, CCM and CPM with non-polarisable force fields (NPFF) generally produce consistent results on ion layering and composition, although differences in ion orientation are observed. However, hybrid IL with a cosolvent exhibit notable discrepancies in solvent behaviour. For mixed-cation ILs, additional caution is required as distinct interfacial responses emerge between NPFF and polarisable force fields (PFF) treatments. This work provides practical guidance for modelling IL-electrode interfaces and highlights the need for careful methodological choice alongside experimental validation.
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BibTeX
@article{ravindranath2026systematic,
title = {{Systematic Investigation of Classical Molecular Dynamics Models for Ionic Liquid‐Based Electrolytes at Electrode Interfaces}},
author = {Sreehari Batni Ravindranath and Jhonatan Soto Puelles and Agílio Pádua and Maria Forsyth and Fangfang Chen},
journal = {ChemPhysChem},
year = {2026},
month = may,
doi = {10.1002/cphc.70431},
url = {https://hal.science/hal-05783616v1},
note = {CC BY-NC},
}
RIS
TY - JOUR
TI - Systematic Investigation of Classical Molecular Dynamics Models for Ionic Liquid‐Based Electrolytes at Electrode Interfaces
AU - Sreehari Batni Ravindranath
AU - Jhonatan Soto Puelles
AU - Agílio Pádua
AU - Maria Forsyth
AU - Fangfang Chen
PY - 2026
DA - 2026/05/27
JO - ChemPhysChem
DO - 10.1002/cphc.70431
UR - https://hal.science/hal-05783616v1
AB - Molecular dynamics (MD) simulations are widely used to investigate ionic liquid (IL) electrolytes and their interfaces at electrified electrodes. However, the predicted interfacial nanostructure and chemistry of electrolytes are strongly influenced by methodological choices, including electrode models and force-field treatments, whose relative performance remains insufficiently understood. Here, we systematically evaluate two electrode modelling approaches: the constant charge model (CCM) and the constant potential model (CPM), together with the role of force field polarisability, for studying interfaces of IL-based electrolytes, including neat ILs, salt-containing ILs, and hybrid systems with cosolvents or mixed cations. The aim is to assess how effective these approaches capture potential-dependent interfacial structure and chemistry relevant to battery performance. For neat and salt-containing ILs, CCM and CPM with non-polarisable force fields (NPFF) generally produce consistent results on ion layering and composition, although differences in ion orientation are observed. However, hybrid IL with a cosolvent exhibit notable discrepancies in solvent behaviour. For mixed-cation ILs, additional caution is required as distinct interfacial responses emerge between NPFF and polarisable force fields (PFF) treatments. This work provides practical guidance for modelling IL-electrode interfaces and highlights the need for careful methodological choice alongside experimental validation.
SN - 1439-4235
SN - 1439-7641
ER -