Ab initio simulated Van Hove correlation function for time-resolved local dynamics in molten MgCl2

Abstract

Ion dynamics that drive the transport and thermophysical properties of molten salts are poorly understood due to challenges in precisely quantifying the spatial and temporal fluctuations of specific ions in highly disordered systems. While the Van Hove correlation function (VHF) obtained from inelastic neutron scattering (INS) probes these dynamics directly, its interpretation is limited by the inherent species-averaging of experiments, which obscures analysis of key ion transport and solvation mechanisms. Here, ab initio molecular dynamics (AIMD) is used to model the VHF, unravel its partial contributions, and elucidate its underlying ionic transport mechanisms. Slow decorrelation is revealed for oppositely charged ions (Mg2+ and Cl−) caused by ion exchange across the solvation shell between adjoining ionocovalent complexes. Furthermore, transport coefficients are accurately recovered, and connections between macroscopic properties and ion dynamics are revealed. This study demonstrates the potential of ab initio-informed VHF to resolve long-standing challenges in uncovering relationships between picosecond-scale ion dynamics, mechanisms, and emergent physical properties of molten salts.