Achieving accurate entropy and melting point by ab initio molecular dynamics and zentropy theory: Application to fluoride and chloride molten salts

TL;DR

This paper introduces a novel multiscale entropy method combined with ab initio molecular dynamics to accurately predict thermodynamic properties like entropy and melting points of molten salts, matching experimental data.

Contribution

The paper presents a new integrated approach using zentropy theory with AIMD to efficiently compute entropy and melting points from a single simulation trajectory.

Findings

Accurate entropy and melting point predictions for molten salts

Strong agreement with experimental thermodynamic data

Efficient single-trajectory entropy estimation method

Abstract

We have recently developed a breakthrough methodology for rapidly computing entropy in both solids and liquids by integrating a multiscale entropy approach (known as zentropy theory) with molecular dynamics (MD) simulations. This approach enables entropy estimation from a single MD trajectory by analyzing the probabilities of local structural configurations and atomic distributions, effectively addressing the long-standing challenge of capturing configurational entropy. Here, we demonstrate the power of this method by predicting entropies, enthalpies, and melting points for 25 binary and ternary chlorite- and fluoride-based molten salts using ab initio MD (AIMD) simulations. The strong agreement between our predictions and experimental data underscores the potential of this approach to transform computational thermodynamics, offering accurate, efficient, and direct predictions of thermodynamic properties across both solid and liquid phases.