Van der Waals interactions in supercritical water under Earth's mantle conditions

Abstract

The properties of water under high pressure and high temperature (HP-HT) are critical in multiple geochemical processes in deep Earth. Ab initio molecular dynamics (AIMD) is a promising approach to study water under extreme conditions without any empirical parameters. However, the accuracy of AIMD simulations is determined by the exchange-correlation (XC) functional including the dispersion correction used in density functional theory calculations. While van der Waals (vdW) interactions are well known to be critically important for water under ambient conditions, the influence of the dispersion correction on the properties of HP-HT water as found in Earth's mantle remains largely unexplored. To address this, we carried out AIMD simulations for supercritical water at 1, 5, and 10 GPa, and 1000 K. We compared PBE, PBE-D3, RPBE-D3, and SCAN functionals, where D3 means Grimme's D3 dispersion correction. We compared the structural, diffusion, and vibrational properties of water as computed with these XC functionals. Overall, the discrepancies between the functionals are reduced under extreme P-T conditions relative to ambient conditions. PBE and PBE-D3 exhibit higher proton-transfer rates than RPBE-D3 and SCAN, suggesting that while vdW interactions do not significantly affect the water structure under extreme conditions, the oxygen-hydrogen bond strength does influence proton transfer. Our results provide molecular-level insight into water in Earth's mantle and offer valuable guidance for selecting appropriate XC functionals in AIMD simulations of aqueous solutions under extreme conditions.