Title: Development of molecular cluster models to probe pyrite surface reactivity

Journal Article · · Journal of Computational Chemistry
DOI: https://doi.org/10.1002/jcc.27213 · OSTI ID:1997563
 [1];  [2];  [1];  [3]
  1. Department of Microbiology and Cell Biology Montana State University Bozeman Montana USA
  2. Research Initiative for Supra‐Materials, Faculty of Engineering Shinshu University Nagano Japan
  3. Department of Chemistry The University of British Columbia Okanagan, Kelowna British Columbia Canada
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Abstract The recent discovery that anaerobic methanogens can reductively dissolve pyrite and utilize dissolution products as a source of iron and sulfur to meet their biosynthetic demands for these elements prompted the development of atomic‐scale nanoparticle models, as maquettes of reactive surface sites, for describing the fundamental redox steps that take place at the mineral surface during reduction. The given report describes our computational approach for modeling n (FeS 2 ) nanoparticles originated from mineral bulk structure. These maquettes contain a comprehensive set of coordinatively unsaturated Fe (II) sites that are connected via a range of persulfide (S 2 2− ) ligation. In addition to the specific maquettes with n  = 8, 18, and 32 FeS 2 units, we established guidelines for obtaining low‐energy structures by considering the pattern of ionic, covalent, and magnetic interactions among the metal and ligand sites. The developed models serve as computational nano‐reactors that can be used to describe the reductive dissolution mechanism of pyrite to better understand the reactive sites on the mineral, where microbial extracellular electron‐transfer reactions can occur.

Research Organization:
Montana State University, Bozeman, MT (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
SC0020246
OSTI ID:
1997563
Journal Information:
Journal of Computational Chemistry, Journal Name: Journal of Computational Chemistry Journal Issue: 32 Vol. 44; ISSN 0192-8651
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
broken-symmetry DFT calculations
magnetic interactions
maquette chemistry
pyrite nanoparticles
reductive dissolution
surface reactivity