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Spectral signatures of excess-proton waiting and transfer-path dynamics in aqueous hydrochloric acid solutions

Author

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  • Florian N. Brünig

    (Freie Universität Berlin, Department of Physics)

  • Manuel Rammler

    (Freie Universität Berlin, Department of Physics)

  • Ellen M. Adams

    (Ruhr-Universität Bochum, Department of Physical Chemistry II)

  • Martina Havenith

    (Ruhr-Universität Bochum, Department of Physical Chemistry II)

  • Roland R. Netz

    (Freie Universität Berlin, Department of Physics)

Abstract

The theoretical basis for linking spectral signatures of hydrated excess protons with microscopic proton-transfer mechanisms has so far relied on normal-mode analysis. We introduce trajectory-decomposition techniques to analyze the excess-proton dynamics in ab initio molecular-dynamics simulations of aqueous hydrochloric-acid solutions beyond the normal-mode scenario. We show that the actual proton transfer between two water molecules involves for relatively large water-water separations crossing of a free-energy barrier and thus is not a normal mode, rather it is characterized by two non-vibrational time scales: Firstly, the broadly distributed waiting time for transfer to occur with a mean value of 200–300 fs, which leads to a broad and weak shoulder in the absorption spectrum around 100 cm−1, consistent with our experimental THz spectra. Secondly, the mean duration of a transfer event of about 14 fs, which produces a rather well-defined spectral contribution around 1200 cm−1 and agrees in location and width with previous experimental mid-infrared spectra.

Suggested Citation

  • 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.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-31700-x
    DOI: 10.1038/s41467-022-31700-x
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    References listed on IDEAS

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    1. Vasileios Balos & Sho Imoto & Roland R. Netz & Mischa Bonn & Douwe Jan Bonthuis & Yuki Nagata & Johannes Hunger, 2020. "Macroscopic conductivity of aqueous electrolyte solutions scales with ultrafast microscopic ion motions," Nature Communications, Nature, vol. 11(1), pages 1-8, December.
    2. 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.
    3. Jan O. Daldrop & Mattia Saita & Matthias Heyden & Victor A. Lorenz-Fonfria & Joachim Heberle & Roland R. Netz, 2018. "Orientation of non-spherical protonated water clusters revealed by infrared absorption dichroism," Nature Communications, Nature, vol. 9(1), pages 1-7, December.
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