Experimental and theoretical study of the electronic structures of α-PbO and β-PbO2

David J. Payne, Russell G. Egdell, Danny S.L. Law, Per Anders Glans, Timothy Learmonth, Kevin E. Smith, Jinghua Guo, Aron Walsh, Graeme W. Watson

Research output: Contribution to journalArticle

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Abstract

The electronic structures of α-PbO and β-PbO2 have been investigated by X-ray photoemission, X-ray absorption and X-ray emission spectroscopies, supported by bandstructure calculations performed within the framework of density functional theory. The relative intensity of a peak found at the bottom of the valence band for both oxides changes dramatically between Al Kα X-ray photoemission and O K shell X-ray emission spectra, demonstrating that the states associated with this peak possess dominant Pb 6s character. This finding is in accord with partial densities of states derived from bandstructure calculations but is at variance with the conventional view that the Pb 6s states in PbO are close to the Fermi energy and hybridise with empty 6p states to give a metal based directional 6s-6p lone pair. The photoemission onset of β-PbO2 contains a well-defined metallic Fermi edge. The position of the onset structure suggests that the metallic nature of PbO2 arises from occupation of conduction band states above the main valence band, probably arising from oxygen vacancy defects. The conduction electrons of β-PbO2 are strongly perturbed by ionisation of Pb core levels, giving rise to distinctive satellites in core XPS whose energies correspond to those of the conduction electron plasmon.

Original languageEnglish
Pages (from-to)267-277
Number of pages11
JournalJournal of Materials Chemistry
Volume17
Issue number3
DOIs
Publication statusPublished - 2007 Jan 11

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Photoemission
Electronic structure
Valence bands
X rays
Core levels
Electrons
X ray absorption
Oxygen vacancies
Fermi level
Conduction bands
Oxides
Ionization
Density functional theory
X ray photoelectron spectroscopy
Metals
Satellites
Defects

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Chemistry

Cite this

Payne, D. J., Egdell, R. G., Law, D. S. L., Glans, P. A., Learmonth, T., Smith, K. E., ... Watson, G. W. (2007). Experimental and theoretical study of the electronic structures of α-PbO and β-PbO2 Journal of Materials Chemistry, 17(3), 267-277. https://doi.org/10.1039/b612323f
Payne, David J. ; Egdell, Russell G. ; Law, Danny S.L. ; Glans, Per Anders ; Learmonth, Timothy ; Smith, Kevin E. ; Guo, Jinghua ; Walsh, Aron ; Watson, Graeme W. / Experimental and theoretical study of the electronic structures of α-PbO and β-PbO2 In: Journal of Materials Chemistry. 2007 ; Vol. 17, No. 3. pp. 267-277.
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Payne, DJ, Egdell, RG, Law, DSL, Glans, PA, Learmonth, T, Smith, KE, Guo, J, Walsh, A & Watson, GW 2007, 'Experimental and theoretical study of the electronic structures of α-PbO and β-PbO2 ', Journal of Materials Chemistry, vol. 17, no. 3, pp. 267-277. https://doi.org/10.1039/b612323f

Experimental and theoretical study of the electronic structures of α-PbO and β-PbO2 . / Payne, David J.; Egdell, Russell G.; Law, Danny S.L.; Glans, Per Anders; Learmonth, Timothy; Smith, Kevin E.; Guo, Jinghua; Walsh, Aron; Watson, Graeme W.

In: Journal of Materials Chemistry, Vol. 17, No. 3, 11.01.2007, p. 267-277.

Research output: Contribution to journalArticle

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AU - Egdell, Russell G.

AU - Law, Danny S.L.

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AU - Learmonth, Timothy

AU - Smith, Kevin E.

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AU - Walsh, Aron

AU - Watson, Graeme W.

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N2 - The electronic structures of α-PbO and β-PbO2 have been investigated by X-ray photoemission, X-ray absorption and X-ray emission spectroscopies, supported by bandstructure calculations performed within the framework of density functional theory. The relative intensity of a peak found at the bottom of the valence band for both oxides changes dramatically between Al Kα X-ray photoemission and O K shell X-ray emission spectra, demonstrating that the states associated with this peak possess dominant Pb 6s character. This finding is in accord with partial densities of states derived from bandstructure calculations but is at variance with the conventional view that the Pb 6s states in PbO are close to the Fermi energy and hybridise with empty 6p states to give a metal based directional 6s-6p lone pair. The photoemission onset of β-PbO2 contains a well-defined metallic Fermi edge. The position of the onset structure suggests that the metallic nature of PbO2 arises from occupation of conduction band states above the main valence band, probably arising from oxygen vacancy defects. The conduction electrons of β-PbO2 are strongly perturbed by ionisation of Pb core levels, giving rise to distinctive satellites in core XPS whose energies correspond to those of the conduction electron plasmon.

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