English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  L-edge X-ray absorption study of mononuclear vanadium complexes and spectral predictions using a restricted open shell configuration interaction ansatz

Maganas, D., Roemelt, M., Weyhermüller, T., Blume, R., Hävecker, M., Knop-Gericke, A., et al. (2014). L-edge X-ray absorption study of mononuclear vanadium complexes and spectral predictions using a restricted open shell configuration interaction ansatz. Physical Chemistry Chemical Physics, 16(1), 264-276. doi:10.1039/C3CP52711E.

Item is

Basic

show hide
Genre: Journal Article

Files

show Files

Locators

show

Creators

show
hide
 Creators:
Maganas, Dimitrios1, Author              
Roemelt, Michael1, 2, Author              
Weyhermüller, Thomas1, Author              
Blume, Raoul3, 4, Author
Hävecker, Michael3, 4, Author
Knop-Gericke, Axel3, Author
DeBeer, Serena1, 5, Author              
Schlögl, Robert3, 6, Author              
Neese, Frank1, Author              
Affiliations:
1Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
2Department of Chemistry, Frick Laboratory, Princeton University, Princeton, New Jersey 08544, USA, ou_persistent22              
3Inorganic Chemistry Department, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany, ou_persistent22              
4Division Solar Energy Research, Helmholtz-Zentrum Berlin/BESSY II, Albert-Einstein-Str. 15, D-12489 Berlin, Germany, ou_persistent22              
5Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853, USA, ou_persistent22              
6Research Department Schlögl, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023874              

Content

show
hide
Free keywords: -
 Abstract: A series of mononuclear V(V), V(IV) and V(III) complexes were investigated by V L-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The spectra show significant sensitivity to the vanadium oxidation state and the coordination environment surrounding the vanadium center. The L-edge spectra are interpreted with the aid of the recently developed Density Functional Theory/Restricted Open Shell Configuration Interaction Singles (DFT/ROCIS) method. This method is calibrated for the prediction of vanadium L-edges with different hybrid density functionals and basis sets. For the B3LYP/def2-TZVP(-f) and BHLYP/def2-TZVP(-f) functional/basis-set combinations, good to excellent agreement between calculated and experimental spectra is obtained. A treatment of the spin–orbit coupling interaction to all orders is achieved by quasi-degenerate perturbation theory (QDPT), in conjunction with DFT/ROCIS for the calculation of the molecular multiplets while accounting for dynamic correlation and anisotropic covalency. The physical origin of the observed spectral features is discussed qualitatively and quantitatively in terms of spin multiplicities, magnetic sublevels and individual 2p to 3d core level excitations. This investigation is an important prerequisite for future applications of the DFT/ROCIS method to vanadium L-edge absorption spectroscopy and vanadium-based heterogeneous catalysts.

Details

show
hide
Language(s): eng - English
 Dates: 2013-06-282013-10-242014-01-01
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/C3CP52711E
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Physical Chemistry Chemical Physics
  Abbreviation : Phys. Chem. Chem. Phys.
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Cambridge, England : Royal Society of Chemistry
Pages: - Volume / Issue: 16 (1) Sequence Number: - Start / End Page: 264 - 276 Identifier: ISSN: 1463-9076
CoNE: https://pure.mpg.de/cone/journals/resource/954925272413_1