Impact of hierarchical water dipole orderings on the dynamics of aqueous salt solutions

Rui Shi (), Anthony J. Cooper and Hajime Tanaka ()
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Rui Shi: Zhejiang University
Anthony J. Cooper: The University of Tokyo
Hajime Tanaka: The University of Tokyo

Nature Communications, 2023, vol. 14, issue 1, 1-10

Abstract: Abstract Ions exhibit highly ion-specific complex behaviours when solvated in water, which remains a mystery despite the fundamental importance of ion solvation in nature, science, and technology. Here we explain these ion-specific properties by the ion-induced hierarchical dipolar, translational, and bond-orientational orderings of ion hydration shell under the competition between ion-water electrostatic interactions and inter-water hydrogen bonding. We first characterise this competition by a new length λHB(q), explaining the ion-specific effects on solution dynamics. Then, by continuously tuning ion size and charge, we find that the bond-orientational order of the ion hydration shell highly develops for specific ion size and charge combinations. This ordering drastically stabilises the hydration shell; its degree changes the water residence time around ions by 11 orders of magnitude for main-group ions. These findings are fundamental to ionic processes in aqueous solutions, providing a physical principle for electrolyte design and application.

Date: 2023
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DOI: 10.1038/s41467-023-40278-x

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