Ab initio study of MgO under pressure using quasi-harmonic approximation

We examine the dependence of the Gibbs free energy and entropy on pressure and density along MgO isotherm 300 K. Some theoretical works have previously predicted a drastic drop of entropy along MgO isotherms by analyzing existing experimental data and extrapolating them to high pressures. We present first-principle calculations of thermodynamic properties of MgO under pressure using density functional theory and quasi-harmonic approximation. The robustness of our calculations is verified by comparing the calculated and experimental phonon dispersion curves. The comparison with available diamond anvil cell experimental data is also provided. Our estimate for the B1–B2 phase transition is in good agreement with other experimental and theoretical studies. However, our results for entropy along isotherm 300 K do not agree with previous theoretical estimates based upon the integration of thermal expansion coefficient and isothermal bulk modulus by volume. (paper)