X-ray scattering reveals ion clustering of dilute chromium species in molten chloride medium

Enhancing the solar energy storage and power delivery afforded by emerging molten salt-based technologies requires a fundamental understanding of the complex interplay between structure and dynamics of the ions in the high-temperature media. Here we report results from a comprehensive study integrating synchrotron X-ray scattering experiments,ab initiomolecular dynamics simulations and rate theory concepts to investigate the behavior of dilute Cr³⁺metal ions in a molten KCl-MgCl₂salt. Our analysis of experimental results assisted by a hybrid transition state-Marcus theory model reveals unexpected clustering of chromium species leading to the formation of persistent octahedral Cr-Cr dimers in the high-temperature low Cr³⁺concentration melt. Furthermore, our integrated approach shows that dynamical processes in the molten salt system are primarily governed by the charge density of the constituent ions, with Cr³⁺exhibiting the slowest short-time dynamics. These findings challenge several assumptions regarding specific ionic interactions and transport in molten salts, where aggregation of dilute species is not statistically expected, particularly at high temperature.