Solvation of simple ions in water at extreme conditions

The interaction of ions and water at high pressure and temperature plays a critical role in Earth and planetary science yet remains poorly understood. Aqueous fluids affect geochemical properties ranging from water phase stability to mineral solubility and reactivity. Here, we report first-principles molecular dynamics simulations of mono-valent ions (Li⁺, K⁺, Cl^-) as well as NaCl in liquid water at temperatures and pressures relevant to the Earth's upper mantle (11 GPa, 1000 K) and concentrations in the dilute limit (0.44-0.88 m), in the regime of ocean salinity. We find that, at extreme conditions, the average structural and vibrational properties of water are weakly affected by the presence of ions, beyond the first solvation shell, similar to what was observed at ambient conditions. We also find that the ionic conductivity of the liquid increases in the presence of ions by less than an order of magnitude and that the dielectric constant is moderately reduced by at most ∼10% at these conditions. Our findings may aid in the parameterization of deep earth water models developed to describe water-rock reactions.