The nature of the hydrated excess proton in water

Dominik Marx, Mark Tuckerman, Jürg Hutter, Michele Parrinello

Research output: Contribution to journalArticle

Abstract

Explanations for the anomalously high mobility of protons in liquid water began with Grotthuss's idea of 'structural diffusion' nearly two centuries ago. Subsequent explanations have refined this concept by invoking thermal hopping, proton tunnelling or solvation effects. More recently, two main structural models have emerged for the hydrated proton. Eigen proposed the formation of an H9O4 complex in which an H3O core is strongly hydrogen-bonded to three H2O molecules. Zundel, meanwhile, supported the notion of an H5O2/+ complex in which the proton is shared between two H2O molecules. Here we use ab initio path integral simulations to address this question. These simulations include time-independent equilibrium thermal and quantum fluctuations of all nuclei, and determine interatomic interactions from the electronic structure. We find that the hydrated proton forms a fluxional defect in the hydrogenbonded network, with both H9O4 and H5O2/+ occurring only in the sense of 'limiting' or 'ideal' structures. The defect can become delocalized over several hydrogen bonds owing to quantum fluctuations. Solvent polarization induces a small barrier to proton transfer, which is washed out by zero-point motion. The proton can consequently be considered part of a 'low-barrier hydrogen bond, in which tunnelling is negligible and the simplest concepts of transition-state theory do not apply. The rate of proton diffusion is determined by thermally induced hydrogen-bond breaking in the second solvation shell.

Original languageEnglish (US)
Pages (from-to)601-604
Number of pages4
JournalNature
Volume397
Issue number6720
DOIs
StatePublished - Feb 18 1999

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protons
water
hydrogen bonds
solvation
defects
molecules
simulation
electronic structure
nuclei
polarization
hydrogen
liquids
interactions

ASJC Scopus subject areas

  • General

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Marx, D., Tuckerman, M., Hutter, J., & Parrinello, M. (1999). The nature of the hydrated excess proton in water. Nature, 397(6720), 601-604. https://doi.org/10.1038/17579

The nature of the hydrated excess proton in water. / Marx, Dominik; Tuckerman, Mark; Hutter, Jürg; Parrinello, Michele.

In: Nature, Vol. 397, No. 6720, 18.02.1999, p. 601-604.

Research output: Contribution to journalArticle

Marx, D, Tuckerman, M, Hutter, J & Parrinello, M 1999, 'The nature of the hydrated excess proton in water', Nature, vol. 397, no. 6720, pp. 601-604. https://doi.org/10.1038/17579
Marx D, Tuckerman M, Hutter J, Parrinello M. The nature of the hydrated excess proton in water. Nature. 1999 Feb 18;397(6720):601-604. https://doi.org/10.1038/17579
Marx, Dominik ; Tuckerman, Mark ; Hutter, Jürg ; Parrinello, Michele. / The nature of the hydrated excess proton in water. In: Nature. 1999 ; Vol. 397, No. 6720. pp. 601-604.
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