Laubach, Stefan and Schmidt, Peter C. and Thißen, Andreas and Fernandez-Madrigal, Francisco Javier and Wu, Qi-Hui and Jaegermann, Wolfram and Klemm, Matthias and Horn, Siegfried (2007):
Theoretical and experimental determination of the electronic structure of V2O5, reduced V2O5-x and sodium intercalated NaV2O5.
In: Physical Chemistry Chemical Physics, 9 (20), pp. 2564-2576. ISSN 1463-9076,
[Article]
Abstract
In this work the electronic structure of V2O5, reduced V2O5−x (V16O39) and sodium intercalated NaV2O5 has been studied by both theoretical and experimental methods. Theoretical band structure calculations have been performed using density functional methods (DFT). We have investigated the electron density distribution of the valence states, the total density of states (total DOS) and the partial valence band density of states (PVBDOS). Experimentally, amorphous V2O5 thin films have been prepared by physical vapour deposition (PVD) on freshly cleaved highly oriented pyrolytic graphite (HOPG) substrates at room temperature with an initial oxygen understoichiometry of about 4%, resulting in a net stoichiometry of V2O4.8. These films have been intercalated by sodium using vacuum deposition with subsequent spontaneous intercalation (NaV2O5) at room temperature. Resonant V3p–V3d photoelectron spectroscopy (ResPES) experiments have been performed to determine the PVBDOS focusing on the calculation of occupation numbers and the determination of effective oxidation state, reflecting ionicity and covalency of the V–O bonds. Using X-ray absorption near edge spectra (XANES) an attempt is made to visualize the changes in the unoccupied DOS due to sodium intercalation. For comparison measurements on nearly stoichiometric V2O5 single crystals have been performed. The experimental data for the freshly cleaved and only marginally reduced V2O5 single crystals and the NaV2O5 results are in good agreement with the calculated values. The ResPES results for V2O4.8 agree in principle with the calculations, but the trends in the change of the ionicity differ between experiment and theory. Experimentally we find partly occupied V 3d states above the oxygen 2p-like states and a band gap between these and the unoccupied states. In theory one finds this occupation scheme assuming oxygen vacancies in V2O5 and by performing a spin-polarized calculation of an antiferromagnetic ordered NaV2O5.
Item Type: | Article |
---|---|
Erschienen: | 2007 |
Creators: | Laubach, Stefan and Schmidt, Peter C. and Thißen, Andreas and Fernandez-Madrigal, Francisco Javier and Wu, Qi-Hui and Jaegermann, Wolfram and Klemm, Matthias and Horn, Siegfried |
Title: | Theoretical and experimental determination of the electronic structure of V2O5, reduced V2O5-x and sodium intercalated NaV2O5 |
Language: | English |
Abstract: | In this work the electronic structure of V2O5, reduced V2O5−x (V16O39) and sodium intercalated NaV2O5 has been studied by both theoretical and experimental methods. Theoretical band structure calculations have been performed using density functional methods (DFT). We have investigated the electron density distribution of the valence states, the total density of states (total DOS) and the partial valence band density of states (PVBDOS). Experimentally, amorphous V2O5 thin films have been prepared by physical vapour deposition (PVD) on freshly cleaved highly oriented pyrolytic graphite (HOPG) substrates at room temperature with an initial oxygen understoichiometry of about 4%, resulting in a net stoichiometry of V2O4.8. These films have been intercalated by sodium using vacuum deposition with subsequent spontaneous intercalation (NaV2O5) at room temperature. Resonant V3p–V3d photoelectron spectroscopy (ResPES) experiments have been performed to determine the PVBDOS focusing on the calculation of occupation numbers and the determination of effective oxidation state, reflecting ionicity and covalency of the V–O bonds. Using X-ray absorption near edge spectra (XANES) an attempt is made to visualize the changes in the unoccupied DOS due to sodium intercalation. For comparison measurements on nearly stoichiometric V2O5 single crystals have been performed. The experimental data for the freshly cleaved and only marginally reduced V2O5 single crystals and the NaV2O5 results are in good agreement with the calculated values. The ResPES results for V2O4.8 agree in principle with the calculations, but the trends in the change of the ionicity differ between experiment and theory. Experimentally we find partly occupied V 3d states above the oxygen 2p-like states and a band gap between these and the unoccupied states. In theory one finds this occupation scheme assuming oxygen vacancies in V2O5 and by performing a spin-polarized calculation of an antiferromagnetic ordered NaV2O5. |
Journal or Publication Title: | Physical Chemistry Chemical Physics |
Journal volume: | 9 |
Number: | 20 |
Divisions: | 11 Department of Materials and Earth Sciences 11 Department of Materials and Earth Sciences > Material Science 11 Department of Materials and Earth Sciences > Material Science > Surface Science Zentrale Einrichtungen DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue > A - Synthesis DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue > A - Synthesis > Subproject A3: Boundary layers and thin films of ionic conductors: Electronic structure, electrochemical potentials, defect formation and degradation mechanisms DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue > C - Modelling DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue > C - Modelling > Subproject C1: Quantum mechanical computer simulations for electron and defect structure of oxides DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres DFG-Collaborative Research Centres (incl. Transregio) |
Date Deposited: | 04 Aug 2011 08:24 |
Official URL: | http://dx.doi.org/10.1039/b612489e |
Additional Information: | SFB 595 Cooperation A3, C1 |
Identification Number: | doi:10.1039/b612489e |
Export: | |
Suche nach Titel in: | TUfind oder in Google |
![]() |
Send an inquiry |
Options (only for editors)
![]() |
Show editorial Details |