High Pressure Phase Diagram of Beryllium from \emph{Ab Initio} Free Energy Calculations

Abstract

We use first principles molecular dynamics simulations coupled to the thermodynamic integration method to study the hcp-bcc transition and melting of beryllium up to a pressure of 1600~GPa. We derive the melting line by equating solid and liquid Gibbs free energies, and represent it by a Simon Glatzel fit $T_m=1564\text{K}(1+P/(15.6032\text{GPa}){)}^{0.383}$, which is in good agreement with previous two-phase simulations below 6000~K. We also derive the hcp-bcc solid-solid phase boundary and show the quasiharmonic approximation underestimates the stability of the hcp structure, predicting lower transition pressures between hcp and bcc phases. However, our results are consistent with the stability regime predicted by the phonon quasiparticle method. We also predict that hcp-bcc-liquid triple point is located at 164.7~GPa and 4314~K. In addition, we compute the shock Hugoniot curve, and show that it is in good agreement with experiments, intersecting our derived melting curve at $\sim$235~GPa at 4900~K. Finally, we show that an isentropic compression path that intersects the melting curve at both low and high temperature in the liquid regime, can reappear in the solid after a gap as large as 7000~K. Therefore, we predict that a large section of the melting curve could be sampled, in principle, by a ramp compression experiment, where solid and liquid Be would coexist as the sample is compressed.

15 pages, 13 figures

References in corpus (4)

• Shock formation and the ideal shape of ramp compression waves
• Silicate Melting and Vaporization during Rocky Planet Formation
• Path Integral Monte Carlo and Density Functional Molecular Dynamics Simulations of Warm, Dense MgSiO${}_3$
• Magnesium Oxide at Extreme Temperatures and Pressures Studied with First-Principles Simulations

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• Electronic-Entropy-Driven Solid-Solid Phase Transitions in Elemental Metals
• Incorporating Gibbs free energy into interatomic potential fitting
• Comparative analysis for the behavior of beryllium and magnesium crystals at ultrahigh pressures
• Electronic-Entropy-Driven Phase Transitions in Compressed Iron Oxides