English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  Kβ Mainline X-ray Emission Spectroscopy as an Experimental Probe of Metal–Ligand Covalency

Pollock, C. J., Delgado-Jaime, M. U., Atanasov, M., Neese, F., & DeBeer, S. (2014). Kβ Mainline X-ray Emission Spectroscopy as an Experimental Probe of Metal–Ligand Covalency. Journal of the American Chemical Society, 136(26), 9453-9463. doi:10.1021/ja504182n.

Item is

Files

show Files

Locators

show

Creators

show
hide
 Creators:
Pollock, Chistopher J.1, Author           
Delgado-Jaime, Mario Ulises1, Author           
Atanasov, Mihail1, 2, Author           
Neese, Frank1, Author           
DeBeer, Serena1, 3, Author           
Affiliations:
1Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
2Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria, ou_persistent22              
3Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States, ou_persistent22              

Content

show
hide
Free keywords: -
 Abstract: The mainline feature in metal Kβ 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 Kβ mainline XES. Ligand field expressions are derived that describe the behavior of Kβ mainlines for first row transition metals with any dn 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 Kβ 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 Kβ mainlines to metal spin state via the 3p–3d exchange coupling. Further, a quantitative relationship between the splitting of the Kβ mainline features and the metal–ligand covalency is established. Thus, this study furthers the quantitative electronic structural information that can be extracted from Kβ mainline spectroscopy.

Details

show
hide
Language(s): eng - English
 Dates: 2014-04-272014-06-202014-07-02
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ja504182n
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 136 (26) Sequence Number: - Start / End Page: 9453 - 9463 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870