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Microscopic Insights into the Fluorite/Water Interfaces from Vibrational Sum Frequency Generation Spectroscopy

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High Performance Computing in Science and Engineering ´16

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Abstract

Water/mineral interfaces are central to a wide range of environmental and technological processes. In this report we provide a quantitative, molecular-level understanding of the CaF2/water interface using Density Functional Theory-based molecular dynamics simulations. In particular through the comparison of calculated Vibrational Sum Frequency Generation spectra to the experimental ones, we give a structural characterisation of the interface at different pH. At low pH, the surface is positively charged, causing a substantial degree of water ordering. Our results suggest that the surface charge originates from the dissolution of fluoride ions of the topmost layer, rather than from proton adsorption to the surface. At high pH we observe the presence of Ca-OH species pointing into the water. Such OH groups do not establish hydrogen bonds with the surrounding water, and are therefore responsible for the “free OH” signature which is recorded in the Vibrational Sum Frequency Generation spectrum.

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Acknowledgements

This work was supported by the DFG Research Grant SU 752/2-1. All the dynamics were simulated on the supercomputers of the High Performance Computing Center (HLRS) of Stuttgart (Grant 2DSFG).

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Authors and Affiliations

  1. Johannes Gutenberg University Mainz, Staudinger Weg 7, 55099, Mainz, Germany

    Rémi Khatib & Marialore Sulpizi

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  1. Rémi Khatib
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  2. Marialore Sulpizi
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Corresponding author

Correspondence to Marialore Sulpizi .

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Editors and Affiliations

  1. Zentrum für Informationsdienste und Hochleistungsrechnen (ZIH), Technische Universität Dresden, Dresden, Germany

    Wolfgang E. Nagel

  2. Abteilung für Angewandte Mathematik, Universität Freiburg, Freiburg, Germany

    Dietmar H. Kröner

  3. Höchstleistungsrechenzentrum Stuttgart (HLRS), Universität Stuttgart, Stuttgart, Germany

    Michael M. Resch

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Khatib, R., Sulpizi, M. (2016). Microscopic Insights into the Fluorite/Water Interfaces from Vibrational Sum Frequency Generation Spectroscopy. In: Nagel, W.E., Kröner, D.H., Resch, M.M. (eds) High Performance Computing in Science and Engineering ´16. Springer, Cham. https://doi.org/10.1007/978-3-319-47066-5_10

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