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

Wernet, P., Kunnus, K., Schreck, S., Quevedo, W., Kurian, R., Techert, S., et al. (2012). Dissecting local atomic and intermolecular interactions of transition-metal ions in solution with selective X-ray spectroscopy. The Journal of Physical Chemistry Letters, 3(23), 3448-3453. doi:10.1021/jz301486u.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0010-2608-7 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0027-CA8A-2
Genre: Journal Article

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1570044.pdf (Publisher version), 361KB
 
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 Creators:
Wernet, P., Author
Kunnus, K., Author
Schreck, S., Author
Quevedo, W., Author
Kurian, R., Author
Techert, S.1, Author              
de Groot, F. M. F., Author
Odelius, M., Author
Fröhlich, A., Author
Affiliations:
1Research Group of Structural Dynamics of (Bio)Chemical Systems, MPI for biophysical chemistry, Max Planck Society, ou_578564              

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Free keywords: 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
 Abstract: 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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Language(s): eng - English
 Dates: 2012-11-06
 Publication Status: Published online
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 Rev. Method: Peer
 Identifiers: DOI: 10.1021/jz301486u
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Title: The Journal of Physical Chemistry Letters
Source Genre: Journal
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Pages: - Volume / Issue: 3 (23) Sequence Number: - Start / End Page: 3448 - 3453 Identifier: -