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Title: Defective pyrite (100) surface: An ab initio study

Abstract

The structural and electronic properties of sulfur monomeric defects at the FeS{sub 2}(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.

Authors:
 [1];  [2];  [3]
  1. Institute of Structural Chemistry, Chemical Research Center, P.O. Box 17, Budapest 1525 (Hungary)
  2. Dipartimento di Scienza dei Materiali, Universita di Milano-Bicocca, Via Cozzi 53, I-20125 Milano (Italy)
  3. Computational Science, Department of Chemistry and Applied Biosciences, ETH Zurich, USI Campus, Via Giuseppe Buffi 13, 6900 Lugano (Switzerland)
Publication Date:
OSTI Identifier:
20957821
Resource Type:
Journal Article
Resource Relation:
Journal Name: Physical Review. B, Condensed Matter and Materials Physics; Journal Volume: 75; Journal Issue: 16; Other Information: DOI: 10.1103/PhysRevB.75.165406; (c) 2007 The American Physical Society; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; DEFECTS; DENSITY FUNCTIONAL METHOD; GROUND STATES; IRON; IRON SULFIDES; PHOTOELECTRON SPECTROSCOPY; PHOTOEMISSION; PYRITE; REDOX REACTIONS; SPIN; SULFUR; SULFUR IONS; SURFACES

Citation Formats

Stirling, Andras, Bernasconi, Marco, and Parrinello, Michele. Defective pyrite (100) surface: An ab initio study. United States: N. p., 2007. Web. doi:10.1103/PHYSREVB.75.165406.
Stirling, Andras, Bernasconi, Marco, & Parrinello, Michele. Defective pyrite (100) surface: An ab initio study. United States. doi:10.1103/PHYSREVB.75.165406.
Stirling, Andras, Bernasconi, Marco, and Parrinello, Michele. Sun . "Defective pyrite (100) surface: An ab initio study". United States. doi:10.1103/PHYSREVB.75.165406.
@article{osti_20957821,
title = {Defective pyrite (100) surface: An ab initio study},
author = {Stirling, Andras and Bernasconi, Marco and Parrinello, Michele},
abstractNote = {The structural and electronic properties of sulfur monomeric defects at the FeS{sub 2}(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.},
doi = {10.1103/PHYSREVB.75.165406},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
number = 16,
volume = 75,
place = {United States},
year = {Sun Apr 15 00:00:00 EDT 2007},
month = {Sun Apr 15 00:00:00 EDT 2007}
}