Solid–liquid transitions of sodium chloride at high pressures

Abstract

We investigate solid-liquid transitions in NaCl at high pressures using molecular dynamics simulations, including the melting curve and superheating/supercooling as well as solid-solid and liquid-liquid transitions. The first-order B1-B2 (NaCl-CsCl type) transition in solid is observed at high pressures besides continuous liquid structure transitions, which are largely analogous to the B1-B2 transition in solid. The equilibrium melting temperatures (T(m)) up to megabar pressure are obtained from the solid-liquid coexistence technique and the superheating-supercooling hysteresis method. Lindemann's vibrational and Born's mechanical instabilities are found upon melting. The Lindemann frequency is calculated from the vibrational density of states. The Lindemann parameter (fractional root-mean-squared displacement) increases with pressure and approaches a constant asymptotically, similar to the Lennard-Jones system. However, the Lindemann melting relation holds for both B1 and B2 phases to high accuracy as for the Lennard-Jonesium. The B1 and B2 NaCl solids can be superheated by 0.18T(m) and 0.24T(m), and the NaCl liquid, supercooled by 0.22T(m) and 0.32T(m), respectively, at heating or cooling rates of 1 K/s and 1 K/ps. The amount of maximum superheating or supercooling and its weak pressure dependence observed for NaCl are in accord with experiments on alkali halides and with simulations on the Lennard-Jones system and Al.