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  First principles calculations of the structure and V L-edge X-ray absorption spectra of V2O5 using local pair natural orbital coupled cluster theory and spin–orbit coupled configuration interaction approaches

Manganas, D., Roemelt, M., Hävecker, M., Trunschke, A., Knop-Gericke, A., Schlögl, R., et al. (2013). First principles calculations of the structure and V L-edge X-ray absorption spectra of V2O5 using local pair natural orbital coupled cluster theory and spin–orbit coupled configuration interaction approaches. Physical Chemistry Chemical Physics, 15(19), 7260-7276. doi:10.1039/C3CP50709B.

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 Creators:
Manganas, Dimitrios1, Author              
Roemelt, Michael1, Author              
Hävecker, Michael2, 3, Author
Trunschke, Annette2, Author
Knop-Gericke, Axel2, Author
Schlögl, Robert2, 4, Author              
Neese, Frank1, Author              
Affiliations:
1Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
2Inorganic Chemistry Department, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany, ou_persistent22              
3Helmholtz-Zentrum Berlin/BESSY II, Division Solar Energy Research , Albert-Einstein-Str. 15, 12489 Berlin, Germany, ou_persistent22              
4Research Department Schlögl, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023874              

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 Abstract: A detailed study of the electronic and geometric structure of V2O5 and its X-ray spectroscopic properties is presented. Cluster models of increasing size were constructed in order to represent the surface and the bulk environment of V2O5. The models were terminated with hydrogen atoms at the edges or embedded in a Madelung field. The structure and interlayer binding energies were studied with dispersion-corrected local, hybrid and double hybrid density functional theory as well as the local pair natural orbital coupled cluster method (LPNO-CCSD). Convergence of the results with respect to cluster size was achieved by extending the model to up to 20 vanadium centers. The O K-edge and the V L2,3-edge NEXAFS spectra of V2O5 were calculated on the basis of the newly developed Restricted Open shell Configuration Interaction with Singles (DFT-ROCIS) method. In this study the applicability of the method is extended to the field of solid-state catalysis. For the first time excellent agreement between theoretically predicted and experimentally measured vanadium L-edge NEXAFS spectra of V2O5 was achieved. At the same time the agreement between experimental and theoretical oxygen K-edge spectra is also excellent. Importantly, the intensity distribution between the oxygen K-edge and vanadium L-edge spectra is correctly reproduced, thus indicating that the covalency of the metal–ligand bonds is correctly described by the calculations. The origin of the spectral features is discussed in terms of the electronic structure using both quasi-atomic jj coupling and molecular LS coupling schemes. The effects of the bulk environment driven by weak interlayer interactions were also studied, demonstrating that large clusters are important in order to correctly calculate core level absorption spectra in solids.

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Language(s): eng - English
 Dates: 2013-02-152013-03-142013-05-21
 Publication Status: Published in print
 Pages: 17
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/C3CP50709B
 Degree: -

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Title: Physical Chemistry Chemical Physics
  Abbreviation : Phys. Chem. Chem. Phys.
Source Genre: Journal
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Publ. Info: Cambridge, England : Royal Society of Chemistry
Pages: - Volume / Issue: 15 (19) Sequence Number: - Start / End Page: 7260 - 7276 Identifier: ISSN: 1463-9076
CoNE: https://pure.mpg.de/cone/journals/resource/954925272413_1