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Resonant XPS study of the pyrite valence band with implications for molecular orbital contributions

  • H.W. Nesbitt EMAIL logo , I. Uhlig , G.M. Bancroft and R. Szargan
Published/Copyright: March 31, 2015
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American Mineralogist
From the journal American Mineralogist Volume 88 Issue 8-9

Abstract

High-quality valence band X-ray photoelectron spectroscopy (XPS) of vacuum-fractured pyrite (FeS2) was performed using photons from a high resolution undulator beamline. The spectra, collected at photon energies ranging from 50 to 65 eV, span the Fe 3p ionization threshold and reveal the nature of both final state and surface state contributions to the valence band. The lower valence band (1.5 to 10 eV binding energy) reflects primarily S 3p-like direct emission final state contributions. In contrast, the upper valence band (0 to 1.5 eV binding energy) incorporates both a ligand to metal charge transfer and a Fe 3d direct emission final state contribution, the latter perhaps derived in part from surface Fe atoms (a surface chemical state contribution). The results imply that calculations of the pyrite density of states, based on ground state configuration, and without consideration of final state contributions, should reflect closely the XPS valence band structure; this is confirmed by comparison of calculation and collected spectra. Although generally similar to low resolution valence band spectra previously collected, these high resolution spectra show little resonant enhancement of any valence bands above the Fe 3p threshold. The important implication concerns the state of Fe 3dt2g orbitals; the weakness of the direct emission final state (Fe3d5+) contribution and strength of the charge transfer final state contribution to the valence band is explained if Fe 3dt2g-derived orbitals are mixed with S valence orbitals, a possibility predicted by recent theoretical considerations (Eyert et al. 1998). Direct emission final state contributions are, however, observed in the upper valence band (0.40 to 1.3 eV binding energy) and some of the signal may result from surface Fe 3d non-bonding orbitals produced by fracture of the mineral

Received: 2002-3-16
Accepted: 2003-4-14
Published Online: 2015-3-31
Published in Print: 2003-8-1

© 2015 by Walter de Gruyter Berlin/Boston

Articles in the same Issue

  1. Melting of garnet peridotite: Effects of capsules and thermocouples, and implications for the high-pressure mantle solidus
  2. High-resolution and energy-filtered TEM of the interface between hematite and ilmenite exsolution lamellae: Relevance to the origin of lamellar magnetism
  3. The structural evolution of mercury sulfide precipitate: an XAS and XRD study
  4. Synthetic fluid inclusions as recorders of microfracture healing and overgrowth formation rates
  5. Fluid-induced nucleation of (Y+REE)-phosphate minerals within apatite: Nature and experiment. Part II. Fluorapatite
  6. A technique for measuring 3D crystal-size distributions of prismatic microlites in obsidian
  7. TEM investigation of forsterite dendrites
  8. Mechanism and kinetics of element and isotopic exchange mediated by a fluid phase
  9. Chromian spinel during melting experiments of dry peridotite (KLB-1) at 1.0–2.5 GPa
  10. Resonant XPS study of the pyrite valence band with implications for molecular orbital contributions
  11. Petrology and mineralogy of wollastonite- and melilite-bearing paralavas from the Central Apennines, Italy
  12. Variation of antiphase domain size in omphacite: A tool to determine the temperature–time history of eclogites revisited
  13. Compressional and shear wave velocities of ringwoodite γ-Mg2SiO4 to 12 GPa
  14. A vibrational spectroscopic study of the oxidation of pyrite by ferric iron
  15. The atomic arrangement of the ganophyllite-group modulated layer silicates as determined from the orthorhombic dimorph of tamaite, with the elusive 16.8 Å ganophyllite-group superstructure revealed
  16. The crystal structure of chromian kassite from the Saranovskoye deposit, Northern Urals, Russia
  17. Spectroscopic and related evidence on the coloring and constitution of New Zealand jade
  18. Chemical speciation of Ag in galena by EPR spectroscopy
  19. Pressure dependence of melt viscosity in the system NaAlSi3O8-CaMgSi2O6
  20. Molecules in the SiO2-clathrate melanophlogite: A single-crystal Raman study
  21. Mn-rich tourmaline from Austria: structure, chemistry, optical spectra, and relations to synthetic solid solutions
  22. Compositional heterogeneity of olivine in thermally metamorphosed serpentinite from Southwest Japan
  23. Magnetic monitoring of hydrothermal magnetite nucleation-and-growth: Record of magnetic reversals
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https://doi.org/10.2138/am-2003-8-910

Articles in the same Issue

  1. Melting of garnet peridotite: Effects of capsules and thermocouples, and implications for the high-pressure mantle solidus
  2. High-resolution and energy-filtered TEM of the interface between hematite and ilmenite exsolution lamellae: Relevance to the origin of lamellar magnetism
  3. The structural evolution of mercury sulfide precipitate: an XAS and XRD study
  4. Synthetic fluid inclusions as recorders of microfracture healing and overgrowth formation rates
  5. Fluid-induced nucleation of (Y+REE)-phosphate minerals within apatite: Nature and experiment. Part II. Fluorapatite
  6. A technique for measuring 3D crystal-size distributions of prismatic microlites in obsidian
  7. TEM investigation of forsterite dendrites
  8. Mechanism and kinetics of element and isotopic exchange mediated by a fluid phase
  9. Chromian spinel during melting experiments of dry peridotite (KLB-1) at 1.0–2.5 GPa
  10. Resonant XPS study of the pyrite valence band with implications for molecular orbital contributions
  11. Petrology and mineralogy of wollastonite- and melilite-bearing paralavas from the Central Apennines, Italy
  12. Variation of antiphase domain size in omphacite: A tool to determine the temperature–time history of eclogites revisited
  13. Compressional and shear wave velocities of ringwoodite γ-Mg2SiO4 to 12 GPa
  14. A vibrational spectroscopic study of the oxidation of pyrite by ferric iron
  15. The atomic arrangement of the ganophyllite-group modulated layer silicates as determined from the orthorhombic dimorph of tamaite, with the elusive 16.8 Å ganophyllite-group superstructure revealed
  16. The crystal structure of chromian kassite from the Saranovskoye deposit, Northern Urals, Russia
  17. Spectroscopic and related evidence on the coloring and constitution of New Zealand jade
  18. Chemical speciation of Ag in galena by EPR spectroscopy
  19. Pressure dependence of melt viscosity in the system NaAlSi3O8-CaMgSi2O6
  20. Molecules in the SiO2-clathrate melanophlogite: A single-crystal Raman study
  21. Mn-rich tourmaline from Austria: structure, chemistry, optical spectra, and relations to synthetic solid solutions
  22. Compositional heterogeneity of olivine in thermally metamorphosed serpentinite from Southwest Japan
  23. Magnetic monitoring of hydrothermal magnetite nucleation-and-growth: Record of magnetic reversals
  24. High-temperature limits on viscosity of non-Arrhenian silicate melts
  25. First reported sedimentary occurrence of berlinite (AlPO4) in phosphate-bearing sediments from Cioclovina Cave, Romania
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