Abstract
We have performed first-principles molecular dynamics simulations of CaO and CaSiO3 liquids over broad ranges of pressure (0-150 GPa) and temperature (2,500-8,000 K) within density-functional theory. The simulated liquid structure changes considerably on compression with the mean cation-anion coordination numbers increasing nearly linearly with volume. The Ca-O coordination number increases from 5 (7) near the ambient pressure to 8 (10) at high pressure for CaO (CaSiO3) liquid. The Si-O coordination number increases from 4 to 6 over the same pressure regime. Our results show that both liquids are much more compressible than their solid counterparts implying the possibility of liquid-solid density crossovers at high pressure. The Gruneisen parameter of both the liquids increases with pressure, which is opposite in case of crystalline phases. The calculated self-diffusion coefficients strongly depend on temperature and pressure, thereby requiring non-Arrhenian representation with variable activation volume. The diffusivity differences between the two liquids tend to be large at low-temperature and low-pressure regime. Also, comparisons with MgSiO3 liquid suggest that network modifier cations Ca and Mg behave similarly though Ca is more coordinated and more mobile as compared to Mg.