Importance of Electronic Entropy for Machine Learning Interatomic Potentials

Fuente: arXiv
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Autori principali: Petersen, Martin Hoffmann, Lysgaard, Steen, Bhowmik, Arghya, Hippalgaonkar, Kedar, Lastra, Juan Maria Garcia
Natura: Preprint
Pubblicazione: 2026
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author Petersen, Martin Hoffmann
Lysgaard, Steen
Bhowmik, Arghya
Hippalgaonkar, Kedar
Lastra, Juan Maria Garcia
author_facet Petersen, Martin Hoffmann
Lysgaard, Steen
Bhowmik, Arghya
Hippalgaonkar, Kedar
Lastra, Juan Maria Garcia
contents Machine learning interatomic potentials (MLIPs) enable large-scale atomistic simulations but remain challenged in describing mixed-valence materials where charge ordering strongly influences thermodynamic stability. Here we investigate the role of electronic entropy in MLIP structural optimization of the battery cathode material \ce{NaFePO4}. We show that conventional MLIPs fail to reproduce the correct stability of intermediate \ce{Na} concentrations because structural optimization leads to incorrect \ce{Fe^{2+}}/\ce{Fe^{3+}} charge assignments, resulting in erroneous energy ordering and convex-hull predictions. Analysis of magnetic moments during structural optimization reveals that MLIPs are unable to capture electronic entropy associated with charge ordering. To address this limitation, we introduce an approach that embeds charge-state information directly into the MLIP representation by distinguishing between \ce{Fe^{2+}} and \ce{Fe^{3+}} environments during training. Retraining CHGNet, cPaiNN, and MACE with this representation enables accurate structural optimization, correct identification of charge ordering, and improved agreement with density functional theory convex hulls. Our results demonstrate that incorporating electronic entropy into MLIP representations is essential for modeling charge-disordered materials and provide a practical framework for extending MLIP simulations to mixed-valence transition-metal systems.
format Preprint
id arxiv_https___arxiv_org_abs_2603_26471
institution arXiv
publishDate 2026
record_format arxiv
spellingShingle Importance of Electronic Entropy for Machine Learning Interatomic Potentials
Petersen, Martin Hoffmann
Lysgaard, Steen
Bhowmik, Arghya
Hippalgaonkar, Kedar
Lastra, Juan Maria Garcia
Materials Science
Computational Physics
Machine learning interatomic potentials (MLIPs) enable large-scale atomistic simulations but remain challenged in describing mixed-valence materials where charge ordering strongly influences thermodynamic stability. Here we investigate the role of electronic entropy in MLIP structural optimization of the battery cathode material \ce{NaFePO4}. We show that conventional MLIPs fail to reproduce the correct stability of intermediate \ce{Na} concentrations because structural optimization leads to incorrect \ce{Fe^{2+}}/\ce{Fe^{3+}} charge assignments, resulting in erroneous energy ordering and convex-hull predictions. Analysis of magnetic moments during structural optimization reveals that MLIPs are unable to capture electronic entropy associated with charge ordering. To address this limitation, we introduce an approach that embeds charge-state information directly into the MLIP representation by distinguishing between \ce{Fe^{2+}} and \ce{Fe^{3+}} environments during training. Retraining CHGNet, cPaiNN, and MACE with this representation enables accurate structural optimization, correct identification of charge ordering, and improved agreement with density functional theory convex hulls. Our results demonstrate that incorporating electronic entropy into MLIP representations is essential for modeling charge-disordered materials and provide a practical framework for extending MLIP simulations to mixed-valence transition-metal systems.
title Importance of Electronic Entropy for Machine Learning Interatomic Potentials
topic Materials Science
Computational Physics
url https://arxiv.org/abs/2603.26471