Disentangling the Discrepancy Between Theoretical and Experimental Curie Temperatures in Ferroelectric PbTiO$_3$

Fuente: arXiv
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Main Authors: Li, Denan, Ahart, Chris, Liu, Shi
Format: Preprint
Published: 2026
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author Li, Denan
Ahart, Chris
Liu, Shi
author_facet Li, Denan
Ahart, Chris
Liu, Shi
contents Accurately predicting the Curie temperature ($T_c$) of ferroelectrics from first principles remains a major challenge, as theoretical estimates often fall significantly below experimental values. In this work, we investigate the origin of these discrepancies in the prototypical ferroelectric PbTiO$_3$ by performing extensive constant-pressure ab initio molecular dynamics (AIMD) simulations and benchmarking them against classical molecular dynamics (MD) using machine learning force fields (MLFFs) derived from first-principles data. Our results show that the underestimation of $T_c$ primarily stems from the limitations of the exchange-correlation functional, rather than inaccuracies in the MLFF fitting. We uncover a critical interplay between finite-size effects and the range of interatomic interactions: although short-range MLFFs appear to yield better agreement with experimental $T_c$, this improvement results from a fortuitous cancellation of errors. Incorporating explicit long-range interactions improves accuracy for larger supercells but ultimately leads to lower predicted $T_c$ values. These findings highlight that accurate finite-temperature predictions require not only high-quality training data and sufficiently large simulation cells, but also the explicit treatment of long-range interactions and improved exchange-correlation functionals.
format Preprint
id arxiv_https___arxiv_org_abs_2601_13125
institution arXiv
publishDate 2026
record_format arxiv
spellingShingle Disentangling the Discrepancy Between Theoretical and Experimental Curie Temperatures in Ferroelectric PbTiO$_3$
Li, Denan
Ahart, Chris
Liu, Shi
Materials Science
Computational Physics
Accurately predicting the Curie temperature ($T_c$) of ferroelectrics from first principles remains a major challenge, as theoretical estimates often fall significantly below experimental values. In this work, we investigate the origin of these discrepancies in the prototypical ferroelectric PbTiO$_3$ by performing extensive constant-pressure ab initio molecular dynamics (AIMD) simulations and benchmarking them against classical molecular dynamics (MD) using machine learning force fields (MLFFs) derived from first-principles data. Our results show that the underestimation of $T_c$ primarily stems from the limitations of the exchange-correlation functional, rather than inaccuracies in the MLFF fitting. We uncover a critical interplay between finite-size effects and the range of interatomic interactions: although short-range MLFFs appear to yield better agreement with experimental $T_c$, this improvement results from a fortuitous cancellation of errors. Incorporating explicit long-range interactions improves accuracy for larger supercells but ultimately leads to lower predicted $T_c$ values. These findings highlight that accurate finite-temperature predictions require not only high-quality training data and sufficiently large simulation cells, but also the explicit treatment of long-range interactions and improved exchange-correlation functionals.
title Disentangling the Discrepancy Between Theoretical and Experimental Curie Temperatures in Ferroelectric PbTiO$_3$
topic Materials Science
Computational Physics
url https://arxiv.org/abs/2601.13125