Melting Behavior of CaO at High Temperature and Pressure: A Molecular Dynamics Study

The thermodynamic behavior of calcium oxide (CaO) under high temperature and pressure conditions is critical for understanding the physics of planetary interiors. This study employs molecular dynamics (MD) simulations, including both classical and ab initio approaches, to investigate the melting behavior of CaO. We calculate the melting temperature of CaO by the void-nucleated melting and two-phase coexistence techniques, aiming to resolve discrepancies in experimental data on the melting point, which range from 2843 to 3223 K in different studies due to the high reactivity and vapor pressure of the substance. The obtained results are Tf = 3066 ± 12 K and Tf = 2940 ± 65 K using the void-nucleated melting and the two-phase coexistence method, respectively. Additionally, we calculate the enthalpy of fusion and the high-pressure melting curve for the first time without making any assumption on the Clapeyron slope. This is extremely important since in experiments, the Clapeyron slope of the melting curve is estimated from low pressure measurements and the overheating ratio (i.e., η=TsTf−1, where Ts represents the thermal instability limit corresponding to the homogeneous melting temperature of the solid) is often assumed to be constant in simulations. Our MD results show that Ts increases more rapidly with pressure than Tf and, thus, that the overheating ratio sensibly depends upon pressure. These findings contribute to accurate modeling of the CaO phase diagram, which is essential for geochemistry, cosmochemistry, and materials science.