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The nature and transport mechanism of hydrated hydroxide ions in aqueous solution

Abstract

Compared to other ions, protons (H+) and hydroxide ions (OH-) exhibit anomalously high mobilities in aqueous solutions1. On a qualitative level, this behaviour has long been explained by ‘structural diffusion’—the continuous interconversion between hydration complexes driven by fluctuations in the solvation shell of the hydrated ions. Detailed investigations have led to a clear understanding of the proton transport mechanism at the molecular level2,3,4,5,6,7,8. In contrast, hydroxide ion mobility in basic solutions has received far less attention2,3,9,10, even though bases and base catalysis play important roles in many organic and biochemical reactions and in the chemical industry. The reason for this may be attributed to the century-old notion11 that a hydrated OH- can be regarded as a water molecule missing a proton, and that the transport mechanism of such a ‘proton hole’ can be inferred from that of an excess proton by simply reversing hydrogen bond polarities11,12,13,14,15,16,17,18. However, recent studies2,3 have identified OH- hydration complexes that bear little structural similarity to proton hydration complexes. Here we report the solution structures and transport mechanisms of hydrated hydroxide, which we obtained from first-principles computer simulations that explicitly treat quantum and thermal fluctuations of all nuclei19,20,21. We find that the transport mechanism, which differs significantly from the proton hole picture, involves an interplay between the previously identified hydration complexes2,3 and is strongly influenced by nuclear quantum effects.

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Figure 1: Schematic illustration of proton and hydroxide ion transport in water at room temperature.
Figure 2: Radial distribution functions and coordination numbers during proton transfer.
Figure 3: Representative configurations showing the proton transfer mechanism.
Figure 4: Structural changes occurring during proton transfer.

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Acknowledgements

M.E.T. was supported by the National Science Foundation (NSF) and Research Corporation.

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Correspondence to Mark E. Tuckerman.

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Tuckerman, M., Marx, D. & Parrinello, M. The nature and transport mechanism of hydrated hydroxide ions in aqueous solution. Nature 417, 925–929 (2002). https://doi.org/10.1038/nature00797

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