The Melting Curve and Premelting of MgO

TL;DR

This study investigates the melting behavior of MgO using molecular dynamics with advanced potentials, revealing a higher melting slope than previous estimates and identifying premelting dynamical features.

Contribution

It provides new ab-initio based melting curve data for MgO and insights into premelting dynamical phenomena using large-scale simulations.

Findings

Melting slope dT/dP is 114 K/GPa, higher than previous estimates.

A low-frequency peak in the dynamical structure factor appears near melting.

Premelting dynamical exchanges may destabilize the crystal.

Abstract

The melting curve for MgO was obtained using molecular dynamics and a non-empirical, many-body potential. We also studied premelting effects by computing the dynamical structure factor in the crystal on approach to melting. The melting curve simulations were performed with periodic boundary conditions with cells up to 512 atoms using the ab-initio Variational Induced Breathing (VIB) model. The melting curve was obtained by computing $% \Delta H_m$ and $\Delta V_m$ and integrating the Clapeyron equation. Our $% \Delta H_m$ is in agreement with previous estimates and we obtain a reasonable $\Delta V_m$, but our melting slope dT/dP (114 K/GPa) is three times greater than that of Zerr and Boehler [1994] (35 K/GPa), suggesting a problem with the experimental melting curve, or an indication of exotic, non-ionic behavior of MgO liquid. We computed $S(q,\omega)$ from simulations of 1000 atom clusters using the Potential Induced Breathing (PIB) model. A low frequency peak in the dynamical structure factor $% S(q,\omega)$ arises below the melting point which appears to be related to the onset of bulk many-atom diffusive exchanges. These exchanges may help destabilize the crystalline state and be related to intrinsic crystalline instability suggested in earlier simulations.