Jump to main content
Jump to site search

Issue 1, 2014
Previous Article Next Article

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

Author affiliations

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.

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

Back to tab navigation

Supplementary files

Publication details

The article was received on 28 Jun 2013, accepted on 24 Oct 2013 and first published on 24 Oct 2013


Article type: Paper
DOI: 10.1039/C3CP52711E
Phys. Chem. Chem. Phys., 2014,16, 264-276
  • Open access: Creative Commons BY license
  •   Request permissions

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

    D. Maganas, M. Roemelt, T. Weyhermüller, R. Blume, M. Hävecker, A. Knop-Gericke, S. DeBeer, R. Schlögl and F. Neese, Phys. Chem. Chem. Phys., 2014, 16, 264
    DOI: 10.1039/C3CP52711E

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements