Iron under Earth’s core conditions: Liquid-state thermodynamics and high-pressure melting curve fromab initiocalculations

Abstract

{\em Ab initio} techniques based on density functional theory in the projector-augmented-wave implementation are used to calculate the free energy and a range of other thermodynamic properties of liquid iron at high pressures and temperatures relevant to the Earth's core. The {\em ab initio} free energy is obtained by using thermodynamic integration to calculate the change of free energy on going from a simple reference system to the {\em ab initio} system, with thermal averages computed by {\em ab initio} molecular dynamics simulation. The reference system consists of the inverse-power pair-potential model used in previous work. The liquid-state free energy is combined with the free energy of hexagonal close packed Fe calculated earlier using identical {\em ab initio} techniques to obtain the melting curve and volume and entropy of melting. Comparisons of the calculated melting properties with experimental measurement and with other recent {\em ab initio} predictions are presented. Experiment-theory comparisons are also presented for the pressures at which the solid and liquid Hugoniot curves cross the melting line, and the sound speed and Gr\"{u}neisen parameter along the Hugoniot. Additional comparisons are made with a commonly used equation of state for high-pressure/high-temperature Fe based on experimental data.