Coordination numbers and physical properties in molten salts and their mixtures

Abstract

Mixtures of trivalent metal halides with alkali halides are involved in many technologies but, from a more fundamental and general perspective, are worthy of study as interesting systems in which to examine the relationship between atomic-scale structure and physical properties. Here we examine the relationship between the viscosity and local and longer range structural measures in such mixtures where the trivalent metal cations span a significant size range and exhibit different behaviours in the dependence of their viscosity on the mixture composition. We characterise the structure and dynamics of the first coordination shell and the relationship between its structural relaxation time and the shear relaxation time of the mixture (the Maxwell relaxation time). We are then led to an examination of the structure of the networks which progressively form between the trivalent metal cations as their concentration increases in the mixtures. Here we find significant differences between small and larger cations, sufficient to explain the different behaviour of their viscosities. We draw attention to the similarities and differences of these networks with those which form in highly viscous, glass-forming materials like BeF₂:LiF.