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

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Maganas,  Dimitrios
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Roemelt,  Michael
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;
Department of Chemistry, Frick Laboratory, Princeton University;

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Weyhermüller,  Thomas
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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DeBeer,  Serena
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;
Department of Chemistry and Chemical Biology, Cornell University;

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Schlögl,  Robert
Inorganic Chemistry Department, Fritz-Haber-Institut der Max-Planck-Gesellschaft;
Research Department Schlögl, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Neese,  Frank
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Citation

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.


Cite as: http://hdl.handle.net/21.11116/0000-0007-A3AB-0
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.