Automated Prediction of Thermodynamic Properties via Bayesian Free-Energy Reconstruction from Molecular Dynamics

TL;DR

This paper introduces an automated, uncertainty-aware workflow that reconstructs free-energy surfaces from molecular dynamics data using Gaussian Process Regression, applicable to both crystalline and liquid phases, improving thermodynamic property predictions.

Contribution

It presents a unified, automated method combining GPR with zero-point energy corrections and active learning to accurately predict thermodynamic properties from MD data.

Findings

Successfully applied to nine elemental metals with quantified confidence intervals.

Demonstrated accurate predictions of heat capacities, thermal expansion, and bulk moduli.

Provided a systematic benchmark for interatomic potentials.

Abstract

Accurate free-energy calculations are essential for predicting thermodynamic properties and phase stability, but existing methods are limited: phonon-based approaches neglect anharmonicity and liquids, while molecular dynamics (MD) is computationally demanding, neglects low-temperature quantum effects, and often requires manual planning and post-processing of simulations. We present a unified workflow that reconstructs the Helmholtz free-energy surface from MD data using Gaussian Process Regression (GPR), augmented with zero-point energy corrections from harmonic/quasi-harmonic theory. The framework propagates statistical uncertainties, mitigates finite-size effects, and employs active learning to optimize sampling in the volume-temperature space. It applies seamlessly to both crystalline and liquid phases. We demonstrate the methodology by computing heat capacities, thermal expansion, isothermal and adiabatic bulk moduli, and melting properties for nine elemental FCC and BCC metals using 20 classical and machine-learned interatomic potentials, with all predictions accompanied by quantified confidence intervals. Automated, general, and uncertainty-aware, the workflow advances high-throughput thermodynamics and provides a systematic benchmark for interatomic potentials.