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 |
Year of first publication: | 2020 |
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 |
ROR: | https://ror.org/023b0x485 |
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 |
Files in This Item:
File | Description | Size | Format | ||
---|---|---|---|---|---|
dr._lesnicki_dominika-surface_charge-20210804001010568.pdf | 2.09 MB | Adobe PDF | View/Open |