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Ionic charge dependence of ion-solvent ICD time-scale for aqueous ions probed by the core-hole clock
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Surface and Interface Science.
Theoretische Chemie, Physikalisch-Chemisches Institut, UniVersität Heidelberg.
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Surface and Interface Science.
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Surface and Interface Science.
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

Auger electron spectroscopy combined with theoretical calculations have been applied to investigate the decay of the Ca 2p core hole of aqueous Ca2+. Localized final states due to Auger-like and de-localized final states due to ICD-like decay processes are identified. By applying the core-hole clock spectroscopy method, the time constant of the ICD-like decay was determined to 24±6 fs for Ca2+. We have compared to ICD-like processes in other aqueous ions, K+, Na+, Mg2+ and Al3+, and observe a variation of the time constants of two orders of magnitude. This large variation is qualitatively explained by differences both internal and external to the ions; different internal decay mechanisms of the ions, as well as external differences in the ion-solute distances and interactions.

National Category
Condensed Matter Physics
Research subject
Physics with spec. in Atomic, Molecular and Condensed Matter Physics
Identifiers
URN: urn:nbn:se:uu:diva-138742OAI: oai:DiVA.org:uu-138742DiVA: diva2:379724
Available from: 2010-12-19 Created: 2010-12-19 Last updated: 2011-04-11
In thesis
1. Solvent–Solute Interaction: Studied by Synchrotron Radiation Based Photo and Auger Electron Spectroscopies
Open this publication in new window or tab >>Solvent–Solute Interaction: Studied by Synchrotron Radiation Based Photo and Auger Electron Spectroscopies
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Aqueous solutions were studied using photoelectron and Auger spectroscopy, based on synchrotron radiation and a liquid micro-jet setup.

By varying the photon energy in photoelectron spectra, we depth profiled an aqueous tetrabutylammonium iodide (TBAI) solution. Assuming uniform angular emission from the core levels, we found that the TBA+ ions were oriented at the surface with the hydrophobic butyl arms sticking into the liquid.

We investigated the association between ions and their neighbors in aqueous solutions by studying the electronic decay after core ionization. The (2p)−1 decay of solvated K+ and Ca2+ ions was studied. The main features in the investigated decay spectra corresponded to two-hole final states localized on the ions. The spectra also showed additional features, related to delocalized two-hole final states with vacancies on a cation and a neighboring water molecule. These two processes compete, and by comparing relative intensities and using the known rate for the localized decay, we determined the time-scale for the delocalized process for the two ions. We compared to delocalized electronic decay processes in Na+, Mg2+, and Al3+, and found that they were slower in K+ and Ca2+, due to different internal decay mechanisms of the ions, as well as external differences in the ion-solute distances and interactions.

In the O 1s Auger spectra of aqueous metal halide solutions, we observed features related to delocalized two-hole final states with vacancies on a water molecule and a neighboring solvated anion. The relative intensity of these feature indicated that the strength of the interaction between the halide ions and water correlated with ionic size.

The delocalized decay was also used to investigate contact ion pair formation in high concentrated potassium halide solutions, but no concrete evidence of contact ion pairs was observed.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2011. 73 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 796
Keyword
Interatomic Coulombic Decay, ICD, Auger electron spectroscopy, AES, X-ray photoelectron spectroscopy, XPS, Ultra-violet spectroscopy, UPS, localized, delocalized, double ionization potential, DIP, two hole, final states, Water, H2O, Potassium chloride, KCl, Calcium chloride, CaCl2, Ammonium, NH4, Core hole, clock, lifetime, solvated, ion, alkali, halide, Coster Kronig, MAX-lab, BESSY
National Category
Condensed Matter Physics
Research subject
Physics with spec. in Atomic, Molecular and Condensed Matter Physics
Identifiers
urn:nbn:se:uu:diva-138749 (URN)978-91-554-7980-0 (ISBN)
Public defence
2011-02-04, Häggsalen, Ångström laboratoriet, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
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Supervisors
Note
Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 726Available from: 2011-01-14 Created: 2010-12-19 Last updated: 2011-03-21Bibliographically approved

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