• search hit 1 of 1
Back to Result List

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.

Export metadata

Additional Services

Search Google Scholar Statistics
Metadaten
Author details:Philippe Wernet, Kristjan KunnusORCiD, Simon Schreck, Wilson Quevedo, Reshmi Kurian, Simone Techert, Frank M. F. de Groot, Michael OdeliusORCiD, Alexander FöhlischORCiDGND
DOI:https://doi.org/10.1021/jz301486u
ISSN:1948-7185
Title of parent work (English):The journal of physical chemistry letters
Publisher:American Chemical Society
Place of publishing:Washington
Publication type:Article
Language:English
Year of first publication:2012
Publication year:2012
Release date:2017/03/26
Volume:3
Issue:23
Number of pages:6
First page:3448
Last Page:3453
Funding institution:Swedish Research Council; Carl Tryggers Foundation; Magnus Bergvall Foundation
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Biochemie und Biologie
Peer review:Referiert
Accept ✔
This website uses technically necessary session cookies. By continuing to use the website, you agree to this. You can find our privacy policy here.