Structure and transport properties of LiF-BeF2 mixtures: Comparison of rigid and polarizable ion potentials

Abstract

Molecular dynamics simulations are performed to study the structure and dynamics of the LiF-BeF2 system over a range of compositions using the transferable rigid-ion model (TRIM). The densities obtained with the TRIM potential are approximately 17-20% lower than the experimental values while polarizable ion models (PIM) give densities within 5% of the experimental value. The TRIM and PIM potentials give essentially identical radial distribution functions (RDFs) for Li-F and Be-F ion pairs though the Be-Be pair correlations differ significantly and reflect the corresponding density differences. The variation in the radial distribution functions with concentration, particularly the anion-anion pair correlation function, reflects the reorganization of the fluoride ions as the addition of BeF2 in the mixture promotes the formation of the tetrahedral fluoroberyllate network. Along the 67 mol% LiF isopleth, diffusivities and Nernst-Einstein ionic conductivities from simulations using the PIM and TRIM potentials are in good agreement for temperatures up to 925 K. The viscosity data using the PIM model is also found to be in good agreement with the TRIM results presented here along the 873K isotherm for compositions ranging from 0 to 50 mol% BeF2. The main conclusion from this study is that the non-polarizable, TRIM provides reasonable results for the structural correlations and transport properties of the LiF-BeF2 system in comparison with first-principles-based, PIM. © Indian Academy of Sciences.