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