Computing the Liquidus of Binary Monatomic Salt Mixtures with Direct Simulation and Alchemical Free Energy Methods

We describe and validate a free-energy-based method for computing the liquidus for binary solid–liquid phase diagrams in molecular simulations of monatomic salts. The method is demonstrated by calculating the liquidus for LiCl–KCl and MgCl2–KCl salt mixtures with the polarizable ion model (PIM). The...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2021-09, Vol.125 (38), p.8498-8513
Main Authors: DeFever, Ryan S, Maginn, Edward J
Format: Article
Language:English
Subjects:
A: New Tools and Methods in Experiment and Theory
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Summary:We describe and validate a free-energy-based method for computing the liquidus for binary solid–liquid phase diagrams in molecular simulations of monatomic salts. The method is demonstrated by calculating the liquidus for LiCl–KCl and MgCl2–KCl salt mixtures with the polarizable ion model (PIM). The free-energy-based method is cross-validated with direct coexistence simulations. Both techniques show excellent agreement with one another. Though the predictions of the PIM disagree with experiments, we use our free-energy-based approach to decouple the contributions of liquid mixture nonidealities and pure component solid–liquid equilibrium to the phase diagram. In both mixtures, the PIM accurately reproduces the liquid phase nonidealities but fails to predict the liquidus because it does not accurately predict the pure component melting temperature of LiCl or MgCl2.
ISSN:1089-5639
1520-5215
DOI:10.1021/acs.jpca.1c06107