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Direct evidence of orbital mixing between water and solvated transition-metal ions: an oxygen 1s XAS and DFT study of aqueous system
Stockholm University, Faculty of Science, Department of Physics.
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2003 In: J. Phys. Chem. A, Vol. 107, no 35, 6869-6876 p.Article in journal (Refereed) Published
Place, publisher, year, edition, pages
2003. Vol. 107, no 35, 6869-6876 p.
URN: urn:nbn:se:su:diva-23433OAI: diva2:192073
Part of urn:nbn:se:su:diva-294Available from: 2004-11-18 Created: 2004-11-18Bibliographically approved
In thesis
1. Probing unoccupied electronic states in aqueous solutions
Open this publication in new window or tab >>Probing unoccupied electronic states in aqueous solutions
2004 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Water is one of the most common compounds on earth and is essential for all biological activities. Water has, however, been a mystery for many years due to the large number of unusual chemical and physical properties, e.g. decreased volume during melting and maximum density at 4 °C. The origin of the anomalies behavior is the nature of the hydrogen bond. This thesis will presented an x-ray absorption spectroscopy (XAS) study to reveal the hydrogen bond structure in liquid water.

The x-ray absorption process is faster than a femtosecond and thereby reflects the molecular orbital structure in a frozen geometry locally around the probed water molecules. The results indicate that the electronic structure of liquid water is significantly different from that of the solid and gaseous forms. The molecular arrangement in the first coordination shell of liquid water is actually very similar as the two-hydrogen-bonded configurations at the surface of ice. This discovery suggests that most molecules in liquid water have two-hydrogen-bonded configurations with one donor and one acceptor hydrogen bond compared to the four-hydrogen-bonded tetrahedral structure in ice. This result is controversial since the general picture is that the structure of liquid water is very similar to the structure of ice. The results are, however, consistent with x-ray and neutron diffraction data but reveals serious discrepancies with structures based on current molecular dynamics simulations. The two-hydrogen-bond configuration in liquid water is rigid and heating from 25 °C to 90 °C introduce a minor change in the hydrogen-bonded configurations. Furthermore, XAS studies of water in aqueous solutions show that ion hydration does not affect the hydrogen bond configuration of the bulk. Only water molecules in the close vicinity to the ions show changes in the hydrogen bond formation. XAS data obtained with fluorescence yield are sensitive enough to resolved electronic structure of water molecules in the first hydration sphere and to distinguish between different protonated species. Hence, XAS is a useful tool to provide insight into the local electronic structure of a hydrogen-bonded liquid and it is applied for the first time on water revealing unique information of high importance.

Place, publisher, year, edition, pages
Stockholm: Fysikum, 2004. 59 p.
x-ray absorption, x-ray absorption spectroscopy, XAS, NEXAFS, water, liquid water, aqueous solution, hydrogen bond, hydrogen bond network, local geometry
National Category
Physical Sciences
urn:nbn:se:su:diva-294 (URN)91-7265-974-2 (ISBN)
Public defence
2004-12-09, sal FA32, AlbaNova universitetscentrum, Roslagstullsbacken 21, Stockholm, 13:00
Available from: 2004-11-18 Created: 2004-11-18Bibliographically approved

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