Theoretical study of the aluminum melting curve to very high pressure

Abstract

A detailed theoretical study of the A1 melting curve from normal melting conditions to pressures in the vicinity of 2 Mbar is presented. The analysis is based on two parallel, but distinct, treatments of the metal: the first from rigorous generalized pseudopotential theory involving first-principles nonlocal pseudopotentials and the second from a parametrized local pseudopotential model which has been accurately fit to first-principles band-theory and experimental equation-of-state data. Both treatments utilize full lattice-dynamical calculations of the phonon free energy in the solid, within the harmonic approximation, and fluid variational theory to obtain the free energy of the liquid. Particular attention is focused on the choice of the reference system in implementing the fluid variational theory. It is shown that in A1 the soft-sphere model of Ross produces a lower (and hence more accurate) liquid free energy than either the hard-sphere or one-component-plasma reference systems, and is, moreover, necessary to obtain a reasonable quantitative description of the melting properties. With the soft-sphere system, the two theoretical treatments give results in good overall agreement with each other and with experiment. In particular, melting on the shock Hugoniot is predicted to begin at about 1.2 Mbar and to end at about 1.55 Mbar, in excellent agreement with the recent preliminary measurements of McQueen.