University of Oulu

Saak, Clara-Magdalena; Richter, Clemens; Unger, Isaak; Mucke, Melanie; Nicolas, Christophe; Hergenhahn, Uwe; Caleman, Carl; Huttula, Marko; Patanen, Minna; Björneholm, Olle; Proton dynamics in molecular solvent clusters as an indicator for hydrogen bond network strength in confined geometries, Phys. Chem. Chem. Phys., 2020,22, 3264-3272.

Proton dynamics in molecular solvent clusters as an indicator for hydrogen bond network strength in confined geometries

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Author: Saak, Clara-Magdalena1; Richter, Clemens2; Unger, Isaak1;
Organizations: 1Department for Physics and Astronomy, Uppsala University, Box 516, 751 20 Uppsala, Sweden
2Leibniz Institute of Surface Engineering (IOM), Permoserstr. 15, 04318 Leipzig, Germany
3Synchrotron SOLEIL, L'Orme des Merisiers, Saint-Aubin, BP 48, Gif-sur-Yvette, Cedex, France
4Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
5Center for Free-Electron Laser Science, Deutsches Elektronen-Synchrotron, Notkestr. 85, 22607 Hamburg, Germany
6Nano and Molecular Systems Research Unit, Faculty of Science, University of Oulu, P. O. Box 3000, Finland
Format: article
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 3 MB)
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Language: English
Published: Royal Society of Chemistry, 2020
Publish Date: 2020-04-29


Hydrogen bonding leads to the formation of strong, extended intermolecular networks in molecular liquids such as water. However, it is less well-known how robust the network is to environments in which surface formation or confinement effects become prominent, such as in clusters or droplets. Such systems provide a useful way to probe the robustness of the network, since the degree of confinement can be tuned by altering the cluster size, changing both the surface-to-volume ratio and the radius of curvature. To explore the formation of hydrogen bond networks in confined geometries, here we present O 1s Auger spectra of small and large clusters of water, methanol, and dimethyl ether, as well as their deuterated equivalents. The Auger spectra of the clusters and the corresponding macroscopic liquids are compared and evaluated for an isotope effect, which is due to proton dynamics within the lifetime of the core hole (proton-transfer-mediated charge-separation, PTM-CS), and can be linked to the formation of a hydrogen bond network in the system. An isotope effect is observed in water and methanol but not for dimethyl ether, which cannot donate a hydrogen bond at its oxygen site. The isotope effect, and therefore the strength of the hydrogen bond network, is more pronounced in water than in methanol. Its value depends on the average size of the cluster, indicating that confinement effects change proton dynamics in the core ionised excited state.

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Series: PCCP. Physical chemistry chemical physics
ISSN: 1463-9076
ISSN-E: 1463-9084
ISSN-L: 1463-9076
Volume: 22
Pages: 3264 - 3272
DOI: 10.1039/C9CP06661F
Type of Publication: A1 Journal article – refereed
Field of Science: 116 Chemical sciences
114 Physical sciences
Funding: The authors thank the Synchrotron SOLEIL (project number 20160555 and 20170443) and the Helmholtz-Zentrum Berlin (HZB) for the allocation of synchrotron radiation beamtime, and the local staff at both facilities for their support during the beamtime. [...] Funding from the Swedish Research Council (VR) for the project VR 2018-00740 is acknowledged. CR and UH acknowledge funding by the Deutsche Forschungsgemeinschaft via Forschergruppe FOR1789. MP and MH acknowledge the support of the Academy of Finland. CC acknowledges program-oriented funds of the Helmholtz Association through the Center for Free-Electron Laser Science at Deutsches Elektronen-Synchrotron (DESY). CMS acknowledges funding from the Swedish Foundation for International Cooperation in Research and Higher Education (STINT).
Copyright information: © 2020 The Authors. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.