Defective pyrite (100) surface: An ab initio study

A. Stirling, Marco Bernasconi, Michele Parrinello

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

The structural and electronic properties of sulfur monomeric defects at the Fe S2 (100) surface have been studied by periodic density-functional calculations. We have shown that for a monomeric sulfur bound to an originally fivefold coordinated surface Fe site, the defect core features a triplet electronic ground state with unpaired spins localized on the exposed Fe-S unit. At this site, the iron and sulfur ions have oxidation states +4 and -2, respectively. This defect can be seen as produced via heterolytic bond breaking of the S-S sulfur dimer followed by a Fe-S redox reaction. The calculated sulfur 2p core-level shifts of the monomeric defects are in good agreement with experimental photoemission spectra, which allow a compelling assignment of the different spectroscopic features. The effect of water on the stability of the defective surface has also been studied, and it has been shown that the triplet state is stable against the wetting of the surface. The most important implications of the presence of the monomeric sulfur defect on the reactivity are also discussed.

Original languageEnglish
Article number165406
JournalPhysical Review B - Condensed Matter and Materials Physics
Volume75
Issue number16
DOIs
Publication statusPublished - Apr 10 2007

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Pyrites
pyrites
Sulfur
sulfur
Defects
defects
Core levels
Redox reactions
Photoemission
electronics
Electronic properties
Dimers
Ground state
atomic energy levels
wetting
Density functional theory
Wetting
pyrite
Structural properties
photoelectric emission

ASJC Scopus subject areas

  • Condensed Matter Physics

Cite this

Defective pyrite (100) surface : An ab initio study. / Stirling, A.; Bernasconi, Marco; Parrinello, Michele.

In: Physical Review B - Condensed Matter and Materials Physics, Vol. 75, No. 16, 165406, 10.04.2007.

Research output: Contribution to journalArticle

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