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Molecular layering of water at surfaces and origin of repulsive hydration forces

Abstract

The short-range forces between hydrophilic surfaces in water determine the behaviour of many diverse systems such as the stability of colloidal dispersions1,2 and soap films3, the swelling of clays4 and the interactions of biological membranes5–8 and macromolecules9. So far, all experimental measurements of these forces have indicated that they are repulsive and decay monotonically with distance out to separations of up to 6 nm. These forces, variously termed ‘structural’ or ‘hydration’ forces, arise from the energy needed to dehydrate interacting surfaces which contain ionic or polar species. Here we have measured, in some detail, the short-range hydration force between two molecularly smooth surfaces of mica containing hydrated potassium ions. We find that while the hydration force is overall repulsive it is not monotonic at separations 1.5 nm but exhibits oscillations, that is, alternating maxima and minima with a mean periodicity of 0.25 ± 0.03 nm, roughly the diameter of the water molecule. These results rationalize apparently irreconcilable observations on clay–water systems and go some way towards clarifying the origin and nature of hydration forces.

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Israelachvili, J., Pashley, R. Molecular layering of water at surfaces and origin of repulsive hydration forces. Nature 306, 249–250 (1983). https://doi.org/10.1038/306249a0

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