Home Identification of pyrite valence band contributions using synchrotron-excited X-ray photoelectron spectroscopy
Article
Licensed
Unlicensed Requires Authentication

Identification of pyrite valence band contributions using synchrotron-excited X-ray photoelectron spectroscopy

  • H.W. Nesbitt EMAIL logo , A.G. Berlich , S.L. Harmer , I. Uhlig , G.M. Bancroft and R. Szargan
Published/Copyright: March 28, 2015
Become an author with De Gruyter Brill
Author Information
American Mineralogist
From the journal American Mineralogist Volume 89 Issue 2-3

Abstract

The major contributions to the pyrite valence band have been identified experimentally by monitoring XPS valence band signal intensity as a function of photon (X-ray source) energy. The S-S σ and σ* orbitals are located at about 13 and 16 eV binding energy and are almost exclusively derived from S 3s-S 3s mixing; there is no experimental evidence for a S 3p contribution to these molecular orbital (molecular orbital) values as required for sp3 hybridization. Fe-S σ (Fe 3deg-S 3pz derived) and Fe-S π and π* (Fe 3dt2g-S 3px,y derived) molecular orbitals are identified at Binding Energies (B.E.) less than 8 eV, and are consistent with energies calculated by Eyert et al. (1998). Fe-S π molecular orbital contributions are located in the valence band between about 1.8 and 3 eV and Fe-S π* molecular orbitals contribute between about 0.7 to 1.5 eV binding energy. Contributions observed at the top of the valence band and concentrated between the Fermi level and about 0.6 eV B.E. may be derived from Fe 3deg (non-bonding) orbitals. The experimental data are consistent with these non-bonding contributions being derived from surface Fe species (Fe electronic surface states), and perhaps represent the Fe 3deg “dangling bonds” produced by rupture of Fe-S σ bonds during fracture. The conformity of spectral assignments based on experimental data with band theoretical calculations (of Eyert et al. 1998, using a basis set appropriate to pyrite) indicates that the essential aspects of the pyrite valence band are understood and energetically quantified. Additional study is required to identify positively.

Received: 2003-1-27
Accepted: 2003-7-7
Published Online: 2015-3-28
Published in Print: 2004-2-1

© 2015 by Walter de Gruyter Berlin/Boston

Articles in the same Issue

  1. Composition and I4/m-P42/n phase transition in scapolite solid solutions
  2. Synthesis and characterization of K2Ca5(SO4)6·H2O, the equivalent of görgeyite, a rare evaporite mineral
  3. Phase relations in the system Fe-FeSi at 21 GPa
  4. The speciation of dissolved H2O in dacitic melt
  5. Nucleation and growth kinetics of the α-β transformation in Mg2SiO4determined by in situ synchrotron powder X-ray diffraction
  6. Experimental determination of siderite stability and application to Martian Meteorite ALH84001
  7. Determination of the molar absorption coefficient for the infrared absorption band of CO2in rhyolitic glasses
  8. Crystallographic properties of the calcium phosphate mineral, brushite, by means of First Principles calculations
  9. The crystal structure of jonesite, Ba2(K,Na)[Ti2(Si5Al)O18(H2O)](H2O)n: A first example of titanosilicate with porous double layers
  10. Crystal-chemistry of talc: A near infrared (NIR) spectroscopy study
  11. Synthesis of beryllian sapphirine in the system MgO-BeO-Al2O3-SiO2-H2O and comparison with naturally occurring beryllian sapphirine and khmaralite, Part 2: A chemographic study of Be content as a function of P, T, assemblage and FeMg–1exchange
  12. Spriggite, Pb3[(UO2)6O8(OH)2](H2O)3, a new mineral with β-U3O8–type sheets: Description and crystal structure
  13. Sieve-textured plagioclase in dacitic magma: Interference imaging results
  14. Single crystal raman spectroscopy of cerussite
  15. Sodalite: High-temperature structures obtained from synchrotron radiation and Rietveld refinements
  16. The structure of metahohmannite, Fe3+2[O(SO4)2]⋅4H2O, by in situ synchrotron powder diffraction
  17. High-pressure synchrotron X-ray diffraction study of spessartine and uvarovite: A comparison between different equation of state models
  18. Quantum calculations of the electronic structure and NMR quadrupolar interaction parameters for tugtupite
  19. Identification of pyrite valence band contributions using synchrotron-excited X-ray photoelectron spectroscopy
  20. Micro-Raman studies of gypsum in the temperature range between 9 K and 373 K
  21. A new rare earth disilicate (REE2Si2O7; REE = Dy, Tm, Lu; type-L): Evidence for nonquenchable 10 GPa polymorph with silicon in fivefold trigonal bipyramidal coordination?
  22. Structural variations in the brownmillerite series Ca2(Fe2–xAlx)O5: Single-crystal X-ray diffraction at 25 °C and high-temperature X-ray powder diffraction (25 °C ≤ T ≤ 1000 °C)
  23. Peculiarity and defect structure of the natural and synthetic zeolite mordenite: A single-crystal X-ray study
  24. Model independent phase equilibrium constraints on the ferrosilite activity in the binary Fe-Mg orthopyroxene solid solution
  25. Microstructural study of synthetic sintered diamond and comparison with carbonado, a natural polycrystalline diamond
  26. Structural and chemical response to varying [4]B content in zoned Fe-bearing olenite from Koralpe, Austria
  27. A new dense silica polymorph: A possible link between tetrahedrally and octahedrally coordinated silica
  28. Epitaxial relationships of clinopyroxene-hosted magnetite determined using electron backscatter diffraction (EBSD) technique
https://doi.org/10.2138/am-2004-2-319

Articles in the same Issue

  1. Composition and I4/m-P42/n phase transition in scapolite solid solutions
  2. Synthesis and characterization of K2Ca5(SO4)6·H2O, the equivalent of görgeyite, a rare evaporite mineral
  3. Phase relations in the system Fe-FeSi at 21 GPa
  4. The speciation of dissolved H2O in dacitic melt
  5. Nucleation and growth kinetics of the α-β transformation in Mg2SiO4determined by in situ synchrotron powder X-ray diffraction
  6. Experimental determination of siderite stability and application to Martian Meteorite ALH84001
  7. Determination of the molar absorption coefficient for the infrared absorption band of CO2in rhyolitic glasses
  8. Crystallographic properties of the calcium phosphate mineral, brushite, by means of First Principles calculations
  9. The crystal structure of jonesite, Ba2(K,Na)[Ti2(Si5Al)O18(H2O)](H2O)n: A first example of titanosilicate with porous double layers
  10. Crystal-chemistry of talc: A near infrared (NIR) spectroscopy study
  11. Synthesis of beryllian sapphirine in the system MgO-BeO-Al2O3-SiO2-H2O and comparison with naturally occurring beryllian sapphirine and khmaralite, Part 2: A chemographic study of Be content as a function of P, T, assemblage and FeMg–1exchange
  12. Spriggite, Pb3[(UO2)6O8(OH)2](H2O)3, a new mineral with β-U3O8–type sheets: Description and crystal structure
  13. Sieve-textured plagioclase in dacitic magma: Interference imaging results
  14. Single crystal raman spectroscopy of cerussite
  15. Sodalite: High-temperature structures obtained from synchrotron radiation and Rietveld refinements
  16. The structure of metahohmannite, Fe3+2[O(SO4)2]⋅4H2O, by in situ synchrotron powder diffraction
  17. High-pressure synchrotron X-ray diffraction study of spessartine and uvarovite: A comparison between different equation of state models
  18. Quantum calculations of the electronic structure and NMR quadrupolar interaction parameters for tugtupite
  19. Identification of pyrite valence band contributions using synchrotron-excited X-ray photoelectron spectroscopy
  20. Micro-Raman studies of gypsum in the temperature range between 9 K and 373 K
  21. A new rare earth disilicate (REE2Si2O7; REE = Dy, Tm, Lu; type-L): Evidence for nonquenchable 10 GPa polymorph with silicon in fivefold trigonal bipyramidal coordination?
  22. Structural variations in the brownmillerite series Ca2(Fe2–xAlx)O5: Single-crystal X-ray diffraction at 25 °C and high-temperature X-ray powder diffraction (25 °C ≤ T ≤ 1000 °C)
  23. Peculiarity and defect structure of the natural and synthetic zeolite mordenite: A single-crystal X-ray study
  24. Model independent phase equilibrium constraints on the ferrosilite activity in the binary Fe-Mg orthopyroxene solid solution
  25. Microstructural study of synthetic sintered diamond and comparison with carbonado, a natural polycrystalline diamond
  26. Structural and chemical response to varying [4]B content in zoned Fe-bearing olenite from Koralpe, Austria
  27. A new dense silica polymorph: A possible link between tetrahedrally and octahedrally coordinated silica
  28. Epitaxial relationships of clinopyroxene-hosted magnetite determined using electron backscatter diffraction (EBSD) technique
Sign up now to receive a 20% welcome discount
Institutional Access
How does access work?
Have an idea on how to improve our website?
Please write us.
© 2025 De Gruyter Brill
Downloaded on 9.9.2025 from https://www.degruyterbrill.com/document/doi/10.2138/am-2004-2-319/html
Scroll to top button