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The hydrogen bond in ice probed by soft x-ray spectroscopy and density functional theory
Stockholm University, Faculty of Science, Department of Physics.
Stanford Synchrotron Radiation Laboratory.
Stockholm University, Faculty of Science, Department of Physics.
Stockholm University, Faculty of Science, Department of Physics.
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2005 (English)In: Journal of Chemical Physics, ISSN 1089-7690, Vol. 122, 154505- p.Article in journal (Refereed) Published
Abstract [en]

We combine photoelectron and x-ray absorption spectroscopy with density functional theory to derive a molecular orbital picture of the hydrogen bond in ice. We find that the hydrogen bond involves donation and back-donation of charge between the oxygen lone pair and the O–H antibonding orbitals on neighboring molecules. Together with internal s-p rehybridization this minimizes the repulsive charge overlap of the connecting oxygen and hydrogen atoms, which is essential for a strong attractive electrostatic interaction. Our joint experimental and theoretical results demonstrate that an electrostatic model based on only charge induction from the surrounding medium fails to properly describe the internal charge redistributions upon hydrogen bonding.

Place, publisher, year, edition, pages
American Institute of Physics , 2005. Vol. 122, 154505- p.
Keyword [en]
ice, hydrogen bonds, X-ray absorption spectra, density functional theory, photoelectron spectra, molecular electronic states, oxygen compounds
National Category
Physical Sciences
Research subject
Chemical Physics
URN: urn:nbn:se:su:diva-23413DOI: 10.1063/1.1879752OAI: diva2:191968
Part of urn:nbn:se:su:diva-286Available from: 2004-11-17 Created: 2004-11-17 Last updated: 2010-01-22Bibliographically approved
In thesis
1. Local Structure of Hydrogen-Bonded Liquids
Open this publication in new window or tab >>Local Structure of Hydrogen-Bonded Liquids
2004 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Ordinary yet unique, water is the substance on which life is based. Water seems, at first sight, to be a very simple molecule, consisting of two hydrogen atoms attached to one oxygen. Its small size belies the complexity of its action and its numerous anomalies, central to a broad class of important phenomena, ranging from global current circulation, terrestrial water and CO2 cycles to corrosion and wetting. The explanation of this complex behavior comes from water's unique ability to form extensive three-dimensional networks of hydrogen-bonds, whose nature and structures, in spite of a great deal of efforts involving a plethora of experimental and theoretical techniques, still lacks a complete scientific understanding.

This thesis is devoted to the study of the local structure of hydrogen-bonded liquids, with a particular emphasis on water, taking advantage of a combination of core-level spectroscopies and density functional theory spectra calculations. X-ray absorption, in particular, is found to be sensitive to the local hydrogen-bond environment, thus offering a very promising tool for spectroscopic identification of specific structural configurations in water, alcohols and aqueous solutions. More specifically, the characteristic spectroscopic signature of the broken hydrogen-bond at the hydrogen side is used to analyze the structure of bulk water, leading to the finding that most molecules are arranged in two hydrogen-bond configurations, in contrast to the picture provided by molecular dynamics simulations. At the liquid-vapor interface, an interplay of surface sensitive measurements and theoretical calculations enables us to distinguish a new interfacial species in equilibrium with the gas. In a similar approach the cluster form of the excess proton in highly concentrated acid solutions and the different coordination of methanol at the vacuum interface and in the bulk can also be clearly identified.

Finally the ability of core-level spectroscopies, aided by sophisticated density functional theory calculations, to directly probe the valence electronic structure of a system is used to observe the nature of the interaction between water molecules and solvated ions in solution. Water around transition metal ions is found to interact with the solute via orbital mixing with the metal d-orbitals. The hydrogen-bond between water molecules is explained in terms of electrostatic interactions enhanced by charge rehybridization in which charge transfer between connecting molecules is shown to be fundamental.

Place, publisher, year, edition, pages
Stockholm: Fysikum, 2004. 66 p.
hydrogen-bond, water, ice, density functional theory, DFT, core-level spectroscopies, x-ray absorption
National Category
Physical Chemistry
urn:nbn:se:su:diva-286 (URN)91-7265-969-6 (ISBN)
Public defence
2004-12-08, sal FA32, AlbaNova universitetscentrum, Roslagstullsbacken 21, Stockholm, 10:00
Available from: 2004-11-17 Created: 2004-11-17Bibliographically approved

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Nilsson, A.Pettersson, L.G.M.
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