The effect of dispersion interactions on the properties of LiF in condensed phases

Abstract

Classical molecular dynamics simulations are performed on LiF in the framework of the polarizable ion model. The overlap repulsion and polarization terms of the interaction potential are derived on a purely non-empirical, first-principles basis. For the dispersion, three cases are considered: a first one in which the dispersion parameters are set to zero and two others in which they are included, with different parametrizations. Various thermodynamic, structural and dynamic properties are calculated for the solid and liquid phases. The melting temperature is also obtained from direct coexistence simulations of the liquid and solid phases. Dispersion interactions appear to have an important effect on the densities of both phases and on the melting point, although the liquid properties are not affected when simulations are performed in the NVT ensemble at the experimental density.