X-ray and molecular dynamics study of the temperature-dependent structure of FLiNaK

Abstract

The atomic structure of FLiNaK and its evolution with temperature are examined with x-ray scattering and molecular dynamics (MD) simulations in the temperature range 460–636 °C. In accord with previous studies, it’s observed that the average nearest-neighbor (NN) cation-anion coordination number increases with increasing cation size, going from ∼4 for Li-F to ∼6.4 for K-F. In addition, we find that there is a coupled change in local coordination geometry – going from tetrahedral for Li-F to octahedral for Na to very disordered quasi-cuboidal for K. The varying geometry and coordination distances for the cation-anion pairs cause a relatively constant F-F next-nearest neighbor (NNN) distance of approximately 3.1 Å. This relatively fixed distance allows the F anions to assume an overall correlated structure very similar to that of a hard-sphere liquid with an extended radius which is beyond the normal F ion size but reflects the cation-anion coordination requirements. Careful consideration of the evolution of the experimental atomic distribution functions with increasing temperature shows that the changes in correlation at each distance can be understood within the context of broadening asymmetric neighbor distributions. Within the temperature range studied, the evolution of F-F correlations with increasing temperature is consistent with changes expected in a hard-sphere liquid simply due to decreasing density.