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Dissecting local atomic and intermolecular interactions of transition-metal ions in solution with selective X-ray spectroscopy

  • 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.

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Author:Philippe Wernet, Kristjan Kunnus, Simon Schreck, Wilson Quevedo, Reshmi Kurian, Simone Techert, Frank M. F. de Groot, Michael Odelius, Alexander FöhlischORCiDGND
ISSN:1948-7185 (print)
Parent Title (English):The journal of physical chemistry letters
Publisher:American Chemical Society
Place of publication:Washington
Document Type:Article
Year of first Publication:2012
Year of Completion:2012
Release Date:2017/03/26
First Page:3448
Last Page:3453
Funder:Swedish Research Council; Carl Tryggers Foundation; Magnus Bergvall Foundation
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Biochemie und Biologie
Peer Review:Referiert