Liquid-Vapor Phase Equilibrium in Molten Aluminum Chloride (AlCl3) Enabled by Machine Learning Interatomic Potentials.

Abstract

Molten salts are promising candidates in numerous clean energy applications, where knowledge of thermophysical properties and vapor pressure across their operating temperature ranges is critical for safe operations. Due to challenges in evaluating these properties using experimental methods, fast and scalable molecular simulations are essential to complement the experimental data. In this study, we developed machine learning interatomic potentials (MLIP) to study the AlCl₃ molten salt across varied thermodynamic conditions (T = 473-613 K and P = 2.7-23.4 bar), which allowed us to predict temperature-surface tension correlations and liquid-vapor phase diagram from direct simulations of two-phase coexistence in this molten salt. Two MLIP architectures, a Kernel-based potential and neural network interatomic potential (NNIP), were considered to benchmark their performance for AlCl₃ molten salt using experimental structure and density values. The NNIP potential employed in two-phase equilibrium simulations yields the critical temperature and critical density of AlCl₃ that are within 10 K (∼3%) and 0.03 g/cm³ (∼7%) of the reported experimental values. An accurate correlation between temperature and viscosities is obtained as well. In doing so, we report that the inclusion of low-density configurations in their training is critical to more accurately represent the AlCl₃ system across a wide phase-space. The MLIP trained using PBE-D3 functional in the ab initio molecular dynamics (AIMD) simulations (120 atoms) also showed close agreement with experimentally determined molten salt structure comprising Al₂Cl₆ dimers, as validated using Raman spectra and neutron structure factor. The PBE-D3 as well as its trained MLIP showed better liquid density and temperature correlation for AlCl₃ system when compared to several other density functionals explored in this work. Overall, the demonstrated approach to predict temperature correlations for liquid and vapor densities in this study can be employed to screen nuclear reactors-relevant compositions, helping to mitigate safety concerns.