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Dissecting Local Atomic and Intermolecular Interactions of Transition-Metal Ions in Solution with Selective X-ray Spectroscopy
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2012 (English)In: Journal of Physical Chemistry Letters, ISSN 1948-7185, Vol. 3, no 23, 3448-3453 p.Article in journal (Refereed) Published
Abstract [en]

Determining covalent and charge-transfer contributions to bonding in solution has remained an experimental challenge. Here, the quenching of fluorescence decay channels as expressed in dips in the L-edge X-ray spectra of solvated 3d transition-metal ions and complexes was reported as a probe. With a full set of experimental and theoretical ab initio L-edge X-ray spectra of aqueous Cr3+, including resonant inelastic X-ray scattering, we address covalency and charge transfer for this prototypical transition-metal ion in solution. We dissect local atomic effects from intermolecular interactions and quantify X-ray optical effects. We find no evidence for the asserted ultrafast charge transfer to the solvent and show that the dips are readily explained by X-ray optical effects and local atomic state dependence of the fluorescence yield. Instead, we find, besides ionic interactions, a covalent contribution to the bonding in the aqueous complex of ligand-to-metal charge-transfer character

Place, publisher, year, edition, pages
2012. Vol. 3, no 23, 3448-3453 p.
Keyword [en]
charge transfer to solvent, dark channel fluorescence yield, inverse partial fluorescence yield, total fluorescence yield, resonant inelastic X-ray scattering, transition-metal ion, aqueous solution
National Category
Theoretical Chemistry
Research subject
Chemical Physics
URN: urn:nbn:se:su:diva-85225DOI: 10.1021/jz301486uOAI: diva2:583010
Swedish Research Council
Available from: 2013-01-07 Created: 2013-01-07 Last updated: 2013-01-28Bibliographically approved

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