The phase diagrams of beryllium and magnesium oxide at megabar pressures

Jizhou Wu; Felipe González-Cataldo; François Soubiran; Burkhard Militzer

doi:10.1088/1361-648X/ac4b2a

The phase diagrams of beryllium and magnesium oxide at megabar pressures

J Phys Condens Matter. 2022 Feb 1;34(14). doi: 10.1088/1361-648X/ac4b2a.

Authors

Jizhou Wu¹, Felipe González-Cataldo¹, François Soubiran², Burkhard Militzer^{1

3}

Affiliations

¹ Department of Earth and Planetary Science, University of California, Berkeley, CA 94720, United States of America.
² CEA DAM-DIF, 91297 Arpajon, France.
³ Department of Astronomy, University of California, Berkeley, CA 94720, United States of America.

PMID: 35026747
DOI: 10.1088/1361-648X/ac4b2a

Abstract

We performab initiosimulations of beryllium (Be) and magnesium oxide (MgO) at megabar pressures and compare their structural and thermodynamic properties. We make a detailed comparison of our two recently derived phase diagrams of Be (Wuet al2021Phys. Rev.B104014103) and MgO (Soubiran and Militzer 2020Phys. Rev. Lett.125175701) using the thermodynamic integration technique, as they exhibit striking similarities regarding their shape. We explore whether the Lindemann criterion can explain the melting temperatures of these materials through the calculation of the Debye temperature at high pressure. From our free energy calculations, we find that the melting line of both materials is well represented by the Simon-Glazel fitT_m(P) =T₀(1 +P/a)^1/c, whereT₀= 1564 K,a= 15.8037 GPa andc= 2.4154 for Be, whileT₀= 3010 K,a= 10.5797 GPa andc= 2.8683 for the MgO in the B1. For the B2 phase, we use the valuesa= 26.1163 GPa andc= 2.2426. Both materials exhibit negative Clapeyron slopes on the boundaries between the two solid phases that are strongly affected by anharmonic effects, which also influence the location of the solid-solid-liquid triple point. We find that the quasi-harmonic approximation underestimates the stability range of the low-pressure phases, namely hcp for Be and B1 for MgO. We also compute the phonon dispersion relations at low and high pressure for each of the phases of these materials, and also explore how the phonon density of states is modified by temperature. Finally, we derive secondary shock Hugoniot curves in addition to the principal Hugoniot curve for both materials, and study their offsets in pressure between solid and liquid branches.

Keywords: ab initio molecular dynamics; anharmonicity; condensed matter physics; density functional theory; phase diagram; shock Hugoniot; thermodynamic integration.