Towards Reactive Electrochemical Transport Using the Lattice Boltzmann Method. Part II: Atomistically Informed Non-Ideal Species Transport
4 affiliations
- 1Faculty of Chemistry,, Theoretical Catalysis and Electrochemistry
- 2University of Duisburg–Essen
- 3Cluster of Excellence RESOLV
- 4Center for Nanointegration Duisburg–Essen (CENIDE
Abstract
The lattice Boltzmann method (LBM) provides an efficient framework for simulating species transport in electrochemical systems; however, conventional formulations commonly rely on ideal or dilute-solution descriptions that neglect molecular-scale non-idealities near solid–electrolyte interfaces. In this work, we extend our previously developed LBM formulation to incorporate non-ideal thermodynamic contributions through the excess chemical potential. The resulting formulation retains the original kinetic structure of the LBM, with non-ideal effects introduced through a modified source term in the species transport equation. This treatment provides a general thermodynamic closure through which steric interactions, species-specific interfacial free energies, and, more generally, excess free-energy models can be incorporated within the same transport framework. The formulation is demonstrated for the electrical double layer by progressively introducing finite-size effects and species-specific microscopic interfacial free-energy contributions. The results show that steric interactions substantially limit the large interfacial ion concentrations predicted by the classical point-ion Poisson–Boltzmann description, while microscopic free-energy contributions produce a further reorganization of the ionic distributions and, consequently, of the interfacial charge density and electrostatic potential. Using hypothetical short-ranged free-energy profiles, the calculations further demonstrate that molecular-scale thermodynamic information can generate an electrostatic response extending beyond the spatial range of the microscopic input through the self-consistent redistribution of charge. The present formulation therefore establishes the excess chemical potential as a natural bridge between microscopic interfacial thermodynamics and mesoscopic species transport. Although analytical free-energy profiles are employed here for demonstration, the framework is not restricted to a particular functional form and permits the direct incorporation of speciesspecific free-energy information obtained from molecular or atomistic simulations, providing a route toward atomistically informed LBM simulations of electrochemical transport.
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BibTeX
@misc{tayyebi2026towards,
title = {{Towards Reactive Electrochemical Transport Using the Lattice Boltzmann Method. Part II: Atomistically Informed Non-Ideal Species Transport}},
author = {Ebrahim Tayyebi and Kai S. Exner and ebrahim tayyebi},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008379/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008379/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Towards Reactive Electrochemical Transport Using the Lattice Boltzmann Method. Part II: Atomistically Informed Non-Ideal Species Transport
AU - Ebrahim Tayyebi
AU - Kai S. Exner
AU - ebrahim tayyebi
PY - 2026
DA - 2026/09/06
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008379/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008379/v1
AB - The lattice Boltzmann method (LBM) provides an efficient framework for simulating species transport in electrochemical systems; however, conventional formulations commonly rely on ideal or dilute-solution descriptions that neglect molecular-scale non-idealities near solid–electrolyte interfaces. In this work, we extend our previously developed LBM formulation to incorporate non-ideal thermodynamic contributions through the excess chemical potential. The resulting formulation retains the original kinetic structure of the LBM, with non-ideal effects introduced through a modified source term in the species transport equation. This treatment provides a general thermodynamic closure through which steric interactions, species-specific interfacial free energies, and, more generally, excess free-energy models can be incorporated within the same transport framework. The formulation is demonstrated for the electrical double layer by progressively introducing finite-size effects and species-specific microscopic interfacial free-energy contributions. The results show that steric interactions substantially limit the large interfacial ion concentrations predicted by the classical point-ion Poisson–Boltzmann description, while microscopic free-energy contributions produce a further reorganization of the ionic distributions and, consequently, of the interfacial charge density and electrostatic potential. Using hypothetical short-ranged free-energy profiles, the calculations further demonstrate that molecular-scale thermodynamic information can generate an electrostatic response extending beyond the spatial range of the microscopic input through the self-consistent redistribution of charge. The present formulation therefore establishes the excess chemical potential as a natural bridge between microscopic interfacial thermodynamics and mesoscopic species transport. Although analytical free-energy profiles are employed here for demonstration, the framework is not restricted to a particular functional form and permits the direct incorporation of speciesspecific free-energy information obtained from molecular or atomistic simulations, providing a route toward atomistically informed LBM simulations of electrochemical transport.
ER -