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The interpretation of X-ray absorption spectra of water and ice
Stockholm University, Faculty of Science, Department of Physics.
2002 In: Chem. Phys. Lett., ISSN 0009-2614, Vol. 364, no 3-4, 363-370 p.Article in journal (Refereed) Published
Place, publisher, year, edition, pages
2002. Vol. 364, no 3-4, 363-370 p.
URN: urn:nbn:se:su:diva-23412OAI: diva2:191967
Part of urn:nbn:se:su:diva-286Available from: 2004-11-17 Created: 2004-11-17Bibliographically 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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