Ab Initio Molecular Dynamics Investigation of the Solvation States of Hydrated Ions in Confined Water

Ionic transport in nanoscale channels with a critical size comparable to that of ions and solutes exhibits exceptional performance in water desalination, ion separation, electrocatalysts, and supercapacitors. However, the solvation states (SSs), i.e., the hydration structures and probability distribution, of hydrated ions in nanochannels differ from those in the bulk and the perspective of continuum theory. In this work, we conduct ab initio enhanced-sampling atomistic simulations to investigate the ion-specific SSs of monovalent ions (including Li⁺, Na⁺, K⁺, F^-, Cl^-, and I^-) in the graphene channel with a width of 1 nm. Our findings highlight that the SSs of those ions are primarily determined by ion-water hydration, where ion-wall interactions play a minor role. The distribution of ions in layered confined water is a result of ion-specific hydration, which arises from the synergy of entropy and enthalpy. The free energy barriers for transitions between SSs are on the order of 1k_BT, allowing for modulation through applying external fields or modifying surface properties. As the ion-wall interaction strengthens, as observed in vermiculite and carbides and nitrides of transition metal channels, the probability of near-wall SSs increases. These results help to improve the performance of nanofluidic devices and provide crucial insights for developing accurate force fields of molecular simulations or advanced theoretical approaches for ion dynamics in confined channels.

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