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.
| Original language | English |
|---|---|
| Pages (from-to) | 952-964 |
| Number of pages | 13 |
| Journal | Journal of Physical Chemistry B |
| Volume | 129 |
| Issue number | 3 |
| DOIs | |
| State | Published - Jan 23 2025 |
Funding
The authors would like to thank the NERSC staff, especially Neil Mehta, for software support and assisting with a parallel installation of the DeePMD kit on Perlmutter. We are grateful to Rabi Khanal for his assistance in performing the structure functions calculations. This work was supported by the Office of Materials and Chemical Technologies within the Office of Nuclear Energy, U.S. Department of Energy. This research used resources of the Oak Ridge Leadership Computing Facility at the Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under contract no. DE-AC05-00OR22725. Additionally, this research used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility located at Lawrence Berkeley National Laboratory, operated under contract no. DE-AC02-05CH11231.