Please use this identifier to cite or link to this item: http://doi.org/10.25358/openscience-6251
Authors: Lesnicki, Dominika
Zhang, Zhen
Bonn, Mischa
Sulpizi, Marialore
Backus, Ellen H. G.
Title: Surface charges at the CaF2/water interface allow very fast intermolecular vibrational-energy transfer
Online publication date: 9-Aug-2021
Language: english
Abstract: We investigate the dynamics of water in contact with solid calcium fluoride, where at low pH, localized charges can develop upon fluorite dissolution. We use 2D surface-specific vibrational spectroscopy to quantify the heterogeneity of the interfacial water (D2O) molecules and provide information about the sub-picosecond vibrational-energy-relaxation dynamics at the buried solid/liquid interface. We find that strongly H-bonded OD groups, with a vibrational frequency below 2500 cm−1, display very rapid spectral diffusion and vibrational relaxation; for weakly H-bonded OD groups, above 2500 cm−1, the dynamics slows down substantially. Atomistic simulations based on electronic-structure theory reveal the molecular origin of energy transport through the local H-bond network. We conclude that strongly oriented H-bonded water molecules in the adsorbed layer, whose orientation is pinned by the localized charge defects, can exchange vibrational energy very rapidly due to the strong collective dipole, compensating for a partially missing solvation shell.
DDC: 530 Physik
530 Physics
540 Chemie
540 Chemistry and allied sciences
Institution: Johannes Gutenberg-Universität Mainz
Department: FB 08 Physik, Mathematik u. Informatik
Place: Mainz
DOI: http://doi.org/10.25358/openscience-6251
Version: Published version
Publication type: Zeitschriftenaufsatz
License: CC BY
Information on rights of use: https://creativecommons.org/licenses/by/4.0/
Journal: Angewandte Chemie
59
31
Pages or article number: 13116
13121
Publisher: Wiley-VCH
Publisher place: Weinheim
Issue date: 2020
ISSN: 1521-3773
Publisher URL: https://doi.org/10.1002/anie.202004686
Publisher DOI: 10.1002/anie.202004686
Appears in collections:JGU-Publikationen

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