Macro-Dipole-Constrainted Learning of Atomic Charges for Accurate Electrostatic Potentials at Electrochemical Interfaces

Fuente: arXiv
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Autores principales: Yang, Jing, Li, Bingxin, Mattoso, Samuel, Abdelkawy, Ahmed, Todorova, Mira, Neugebauer, Jörg
Formato: Preprint
Publicado: 2025
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author Yang, Jing
Li, Bingxin
Mattoso, Samuel
Abdelkawy, Ahmed
Todorova, Mira
Neugebauer, Jörg
author_facet Yang, Jing
Li, Bingxin
Mattoso, Samuel
Abdelkawy, Ahmed
Todorova, Mira
Neugebauer, Jörg
contents Large thermal fluctuations of the liquid phase obscure the weak macroscopic electric field that drives electrochemical reactions, rendering the extraction of reliable interfacial charge distributions from ab initio molecular dynamics extremely challenging. We introduce SMILE-CP (Scalar Macro-dipole Integrated LEarning - Charge Partitioning), a macro-dipole-constrained scheme that infers atomic charges using only the instantaneous atomic coordinates and the total dipole moment of the simulation cell - quantities routinely available from standard density-functional theory calculations. SMILE-CP preserves both the global electrostatic field and the local potential without invoking any explicit charge-partitioning scheme. Benchmarks on three representative electrochemical interfaces - nanoconfined water, Mg2+ dissolution in water, and a kinked Mg vicinal surface under anodic bias - show that SMILE-CP eliminates the qualitative errors observed for unconstrained charge decompositions. The method is computationally inexpensive and data-efficient, opening the door to charge-aware machine-learning potentials capable of bias-controlled, nanosecond-scale simulations of realistic electrochemical systems.
format Preprint
id arxiv_https___arxiv_org_abs_2510_01042
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Macro-Dipole-Constrainted Learning of Atomic Charges for Accurate Electrostatic Potentials at Electrochemical Interfaces
Yang, Jing
Li, Bingxin
Mattoso, Samuel
Abdelkawy, Ahmed
Todorova, Mira
Neugebauer, Jörg
Chemical Physics
Materials Science
Large thermal fluctuations of the liquid phase obscure the weak macroscopic electric field that drives electrochemical reactions, rendering the extraction of reliable interfacial charge distributions from ab initio molecular dynamics extremely challenging. We introduce SMILE-CP (Scalar Macro-dipole Integrated LEarning - Charge Partitioning), a macro-dipole-constrained scheme that infers atomic charges using only the instantaneous atomic coordinates and the total dipole moment of the simulation cell - quantities routinely available from standard density-functional theory calculations. SMILE-CP preserves both the global electrostatic field and the local potential without invoking any explicit charge-partitioning scheme. Benchmarks on three representative electrochemical interfaces - nanoconfined water, Mg2+ dissolution in water, and a kinked Mg vicinal surface under anodic bias - show that SMILE-CP eliminates the qualitative errors observed for unconstrained charge decompositions. The method is computationally inexpensive and data-efficient, opening the door to charge-aware machine-learning potentials capable of bias-controlled, nanosecond-scale simulations of realistic electrochemical systems.
title Macro-Dipole-Constrainted Learning of Atomic Charges for Accurate Electrostatic Potentials at Electrochemical Interfaces
topic Chemical Physics
Materials Science
url https://arxiv.org/abs/2510.01042