Water on ceria{111}: Comparison between 23 experimental vibrational studies in the literature and new modeling.

Autor:	Röckert A; Department of Chemistry - Ångström Laboratory, Uppsala University, 751 21 Uppsala, Sweden., Kullgren J; Department of Chemistry - Ångström Laboratory, Uppsala University, 751 21 Uppsala, Sweden., Sethio D; Department of Chemistry - Ångström Laboratory, Uppsala University, 751 21 Uppsala, Sweden., Agosta L; Department of Chemistry - Ångström Laboratory, Uppsala University, 751 21 Uppsala, Sweden., Hermansson K; Department of Chemistry - Ångström Laboratory, Uppsala University, 751 21 Uppsala, Sweden.
Jazyk:	angličtina
Zdroj:	The Journal of chemical physics [J Chem Phys] 2023 Jul 28; Vol. 159 (4).
DOI:	10.1063/5.0147518
Abstrakt:	Theoretical and experimental vibrational signatures of H2O and OH- (dissociated water) adsorbed on stoichiometric ceria{111} surfaces are compared. The experimental ones were collected from low-coverage experiments in the literature, and the theoretical anharmonic frequencies were generated using density functional theory calculations employing the optPBE-vdW functional for coverages from 0.5 to a few monolayers. It is found that (i) the experiments and our calculations overall agree well, lending credibility to both; (ii) the calculations manage to resolve the large class of H-bonded motifs into frequency classes that can guide experimental assignments; (iii) it is possible to find a geometrical H-bond definition that also captures the OH vibrational frequency downshifts well: R(H⋯O) ≤2.5 Å and the O-H⋯O angle θ ≥ 100°; and (iv) the frequency vs electric field relations for water and hydroxides (i.e., dissociated water) follow different and well-separated curves. (© 2023 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).)
Databáze:	MEDLINE
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