English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  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

Maganas, 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.

Item is

Files

show Files
hide Files
:
c3cp50709b.pdf (Any fulltext), 6MB
Name:
c3cp50709b.pdf
Description:
-
OA-Status:
Visibility:
Public
MIME-Type / Checksum:
application/pdf / [MD5]
Technical Metadata:
Copyright Date:
2013
Copyright Info:
RSC

Locators

show

Creators

show
hide
 Creators:
Maganas, Dimitrios1, Author
Roemelt, Michael1, Author
Hävecker, Michael2, 3, Author           
Trunschke, Annette3, Author           
Knop-Gericke, Axel3, Author           
Schlögl, Robert1, 3, Author           
Neese, Frank1, Author
Affiliations:
1Max-Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, Mülheim an der Ruhr, Germany , ou_persistent22              
2Helmholtz-Zentrum Berlin fuer Materialien und Energy GmbH, Division Solar Energy Research, Elektronenspeicherring BESSY II, ou_persistent22              
3Inorganic Chemistry, Fritz Haber Institute, Max Planck Society, ou_24023              

Content

show
hide
Free keywords: -
 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.

Details

show
hide
Language(s): eng - English
 Dates: 2013-02-152013-03-112013-03-142013-05-21
 Publication Status: Issued
 Pages: 17
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/c3cp50709b
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Physical Chemistry Chemical Physics
Source Genre: Journal
 Creator(s):
Affiliations:
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