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The nature of the hydrated excess proton in water

Author

Listed:
  • Dominik Marx

    (Max-Planck-Institut für Festkrperforschung)

  • Mark E. Tuckerman

    (New York University)

  • Jürg Hutter

    (Max-Planck-Institut für Festkrperforschung)

  • Michele Parrinello

    (Max-Planck-Institut für Festkrperforschung)

Abstract

Explanations for the anomalously high mobility of protons in liquid water began with Grotthuss's idea1, 2 of ‘structural diffusion’ nearly two centuries ago. Subsequent explanations have refined this concept by invoking thermal hopping3, 4, proton tunnelling5, 6 or solvation effects7. More recently, two main structural models have emerged for the hydrated proton. Eigen8, 9 proposed the formation of an H9O4+ complex in which an H3O+ core is strongly hydrogen-bonded to three H2O molecules. Zundel10, 11, meanwhile, supported the notion of an H5O2+ complex in which the proton isshared between two H2O molecules. Here we use ab initio path integral12,13,14 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 hydrogen-bonded network, with both H9O4+ and H5O2+ occurring only in thesense 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’15, 16, 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.

Suggested Citation

  • Dominik Marx & Mark E. Tuckerman & Jürg Hutter & Michele Parrinello, 1999. "The nature of the hydrated excess proton in water," Nature, Nature, vol. 397(6720), pages 601-604, February.
  • Handle: RePEc:nat:nature:v:397:y:1999:i:6720:d:10.1038_17579
    DOI: 10.1038/17579
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    Citations

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    Cited by:

    1. Florian N. Brünig & Manuel Rammler & Ellen M. Adams & Martina Havenith & Roland R. Netz, 2022. "Spectral signatures of excess-proton waiting and transfer-path dynamics in aqueous hydrochloric acid solutions," Nature Communications, Nature, vol. 13(1), pages 1-12, December.
    2. Jinfeng Liu & Jinrong Yang & Xiao Cheng Zeng & Sotiris S. Xantheas & Kiyoshi Yagi & Xiao He, 2021. "Towards complete assignment of the infrared spectrum of the protonated water cluster H+(H2O)21," Nature Communications, Nature, vol. 12(1), pages 1-10, December.
    3. Markus Schröder & Fabien Gatti & David Lauvergnat & Hans-Dieter Meyer & Oriol Vendrell, 2022. "The coupling of the hydrated proton to its first solvation shell," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    4. Zhangcai Zhang & Lixin Liang & Jianze Feng & Guangjin Hou & Wencai Ren, 2024. "Significant enhancement of proton conductivity in solid acid at the monolayer limit," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    5. Benbing Shi & Xiao Pang & Shunning Li & Hong Wu & Jianliang Shen & Xiaoyao Wang & Chunyang Fan & Li Cao & Tianhao Zhu & Ming Qiu & Zhuoyu Yin & Yan Kong & Yiqin Liu & Mingzheng Zhang & Yawei Liu & Fen, 2022. "Short hydrogen-bond network confined on COF surfaces enables ultrahigh proton conductivity," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    6. Noor H. Jawad & Ali Amer Yahya & Ali R. Al-Shathr & Hussein G. Salih & Khalid T. Rashid & Saad Al-Saadi & Adnan A. AbdulRazak & Issam K. Salih & Adel Zrelli & Qusay F. Alsalhy, 2022. "Fuel Cell Types, Properties of Membrane, and Operating Conditions: A Review," Sustainability, MDPI, vol. 14(21), pages 1-48, November.

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