Study of NaF–AlF 3 Melts by Coupling Molecular Dynamics, Density Functional Theory, and NMR Measurements

Improvement of the industrial electrolytic process for aluminum production necessitates a thorough understanding of the underlying ionic structure of the electrolyte, which mainly comprises NaF and AlF 3 at around 965 °C. The chemical and physical properties of this melt strongly depend on the aluminum speciation, which requires a multipronged approach in order to clarify its properties. Here we parametrize a new polarizable ion model (PIM) interatomic potential for the molten NaF–AlF 3 system, which is used to study the liquid properties up to 50 mol % of AlF 3 at high temperatures. The potential parameters are obtained by force fitting to density functional theory (DFT) reference data. Molecular dynamics (MD) simulations are combined with further DFT calculations to determine NMR chemical shifts for 27 Al, 23 Na, and 19 F. An excellent agreement is obtained with experimental values. This enables the study of the dynamic properties of the melts such as viscosity, electrical conductivity, and self-diffusion coefficient.