Cation-ligand hybridization for stoichiometric and reduced<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mi mathvariant="normal">TiO</mml:mi></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>(110) surfaces determined by resonant photoemission

Zhang, Zhaoming; Jeng, Shin-Puu; Henrich, Victor E.

doi:10.1103/physrevb.43.12004

Cited by 254 publications

(122 citation statements)

References 34 publications

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“…(Had Ti been completely ionized, there would be no Ti valence-electron emission.) Although early interpretations of the rutile TiO 2 photoelectron spectrum have attributed the valence-electron emission primarily to the O 2p derived valence states [5], our data support more recent resonant-photoemission [7,8], x-ray photoelectrondiffraction [8], and x-ray fluorescence studies [9] that have indicated a significant amount of Ti 3d (and possibly 4s) admixture in the valence band.…”

Section: H Y S I C a L R E V I E W L E T T E R S 12 August 2002supporting

confidence: 76%

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Hybridization and Bond-Orbital Components in Site-Specific X-Ray Photoelectron Spectra of RutileTiO2

et al. 2002

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Section: H Y S I C a L R E V I E W L E T T E R S 12 August 2002supporting

confidence: 76%

“…2, is 17 eV. On the other hand, the energy separation between the Ti 3d, 4s, and 4p atomic orbitals is significantly smaller 8 eV [7,11], accounting for the much larger amount of Ti 3d, 4s, and 4p hybridization observed on the Ti sites.…”

Section: Volume 89 Number 7 P H Y S I C a L R E V I E W L E T T E R mentioning

confidence: 99%

Hybridization and Bond-Orbital Components in Site-Specific X-Ray Photoelectron Spectra of RutileTiO2

et al. 2002

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“…The ultraviolet photoemission spectroscopy ͑UPS͒ spectra contain a band-gap feature for reduced samples which is interpreted in terms of occupied states formed from Ti (3d) orbitals, 1,12 a view supported by the resonant behavior of UPS across the range of photon energies corresponding to the Ti 3p-3d excitation threshold. The shift of the Ti (2p) core levels seen in x-ray photoelectron spectroscopy 13 and the lack of surface conductivity also evidence the localized nature of the additional electrons. Regardless of the location of the oxygen vacancies ͑i.e., in the bulk or at a surface͒ the energy levels of the excess electrons lie in the upper half of the bulk band gap, though their position depends on the degree of reduction.…”

Section: Introductionmentioning

confidence: 99%

First-principles spin-polarized calculations on the reduced and reconstructedTiO2(110) surface

et al. 1997

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We have performed plane-wave pseudopotential density-functional theory calculations on the stoichiometric and reduced TiO 2 ͑110͒ surface, the 2ϫ1 and 1ϫ2 reconstructions of the surface formed by the removal of bridging-oxygen atoms, and on the oxygen vacancy in the bulk. The effect of including spin polarization is investigated, and it is found to give a qualitatively different electronic structure compared with a spin-paired description. In the spin-polarized solutions, the excess electrons generated by oxygen reduction occupy localized band-gap states formed from Ti (3d) orbitals, in agreement with experimental findings. In addition, the inclusion of spin polarization substantially lowers the energy of all the systems studied, when compared with spin-paired solutions. However, spin-polarization does not change the relative stability of the two reconstructions, which remain energetically equivalent. ͓S0163-1829͑97͒02724-0͔

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“…It is known from ultraviolet photoemission spectroscopy (UPS) and electron energy loss spectroscopy (EELS) that the oxygen deficiency defects give rise to gap states lying about 0.7 to 1.0 eV below the conduction band edge [8][9][10][11][12][13]. However, the origin and localisation of these states are still contentious.…”

Section: Introductionmentioning

confidence: 99%

Calculation of point defects in rutile TiO2by the screened-exchange hybrid functional

2012

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The formation energies of the oxygen vacancy and titanium interstitial in rutile TiO 2 were calculated by the screened exchange (sX) hybrid density functional method, which gives a band gap of 3.1 eV, close to the experimental value. The O vacancy gives rise to a gap state lying 0.7 eV below the conduction band edge, whose charge density is localised around the two of three Ti atoms next to the vacancy. The Ti interstitial generates four defect states in the gap, whose unpaired electrons lie on the interstitial and the adjacent Ti 3d orbitals. The formation energy for the neutral O vacancy is 1.9 eV for the O-poor chemical potential, and similar to that of the neutral Ti interstitial, and has a lower formation energy for Ti interstitial under O-rich conditions. This indicates that both the O vacancy and Ti interstitial are relevant for oxygen deficiency in rutile TiO 2 but the O vacancy will dominate under O-rich conditions. This resolves the questions about defect localisation and defect predominance in the literature.

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Cation-ligand hybridization for stoichiometric and reducedTiO2(110) surfaces determined by resonant photoemission

Cited by 254 publications

References 34 publications

Hybridization and Bond-Orbital Components in Site-Specific X-Ray Photoelectron Spectra of RutileTiO2

Hybridization and Bond-Orbital Components in Site-Specific X-Ray Photoelectron Spectra of RutileTiO2

First-principles spin-polarized calculations on the reduced and reconstructedTiO2(110) surface

Calculation of point defects in rutile TiO2by the screened-exchange hybrid functional

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