Probing pH-Dependent Dehydration Dynamics of Mg and Ca Cations in Aqueous Solutions with Multi-Level Quantum Mechanics/Molecular Dynamics Simulations

The dehydration of aqueous calcium and magnesium cations is the most fundamental process controlling their reactivity in chemical and biological phenomena, such as the formation of ionic solids or passing through ion channels. It holds particular relevance in light of recent advancements in the development of carbon capture techniques that rely on mineralization for long-term carbon storage. Specifically, dehydration of Ca2+ and Mg2+ is a key step in proposed carbon capture processes aiming to exploit the relatively high concentration of dissolved carbon dioxide in seawater via the formation of carbonate minerals from solvated Ca2+ and Mg2+ cations for sequestration and storage. Nevertheless, atomic-scale understanding of the dehydration of aqueous Ca2+ and Mg2+ cations remains limited. Here, we utilize rare event sampling via density functional theory molecular dynamics and embedded wavefunction theory calculations to elucidate the dehydration dynamics of aqueous Ca2+ and Mg2+. Emphasis is placed on the investigation of the effect pH has on the stability of the different coordination environments. Our results reveal significant differences in the dehydration dynamics of the two cations and provide insight into how they may be modulated by pH changes.