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          Institute: MPI für bioanorganische Chemie     Collection: MPI für bioanorganische Chemie     Display Documents



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ID: 708880.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
Kβ Mainline X-ray Emission Spectroscopy as an Experimental Probe of Metal-Ligand Covalency.
Authors:Pollock, Christopher J.; Delgado-Jaime, Mario Ulises; Atanasov, Mihail; Neese, Frank; DeBeer, Serena
Language:English
Date of Publication (YYYY-MM-DD):2014
Title of Journal:Journal of the American Chemical Society
Journal Abbrev.:J.Am.Chem.Soc.
Volume:136
Issue / Number:26
Start Page:9453
End Page:9463
Review Status:Peer-review
Audience:Experts Only
Abstract / Description:The mainline feature in metal K beta X-ray emission spectroscopy (XES) has long been recognized as an experimental marker for the spin state of the metal center. However, even within a series of metal compounds with the same nominal oxidation and spin state, significant changes are observed that cannot be explained on the basis of overall spin. In this work, the origin of these effects is explored, both experimentally and theoretically, in order to develop the chemical information content of K beta mainline XES. Ligand field expressions are derived that describe the behavior of K beta mainlines for first row transition metals with any d(n) count, allowing for a detailed analysis of the factors governing mainline shape. Further, due to limitations associated with existing computational approaches, we have developed a new methodology for calculating K beta mainlines using restricted active space configuration interaction (RAS-CI) calculations. This approach eliminates the need for empirical parameters and provides a powerful tool for investigating the effects that chemical environment exerts on the mainline spectra. On the basis of a detailed analysis of the intermediate and final states involved in these transitions, we confirm the known sensitivity of K beta mainlines to metal spin state via the 3p-3d exchange coupling. Further, a quantitative relationship between the splitting of the K beta mainline features and the metal-ligand covalency is established. Thus, this study furthers the quantitative electronic structural information that can be extracted from K beta mainline spectroscopy.
External Publication Status:published
Document Type:Article
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
Identifiers:ISI:000338692700032 [ID No:1]
ISSN:0002-7863 [ID No:2]
DOI:10.1021/ja504182n
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