Vacancy Ordering in Fe-Deficient Iron Sulfide with the NiAs-Type Structure

David Santos-Carballal; Nora H. de Leeuw

doi:10.1021/acs.jpcc.4c05199

Vacancy Ordering in Fe-Deficient Iron Sulfide with the NiAs-Type Structure

David Santos-Carballal^*, Nora H. de Leeuw

^*Corresponding author for this work

University of Leeds

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

An Fe-deficient iron sulfide thin film with a nickeline (NiAs) type structure has been reported with a stoichiometry close to greigite (Fe₃S₄) [ Davis, E. M. ; Phys. Chem. Chem. Phys. 2019, 21, 20204-20210 ]. We have investigated the Fe-vacancy ordering in the nonstoichiometric iron sulfide with the NiAs-like structure using density functional theory calculations with a Hubbard Hamiltonian and long-range dispersion corrections [DFT + U - D3(BJ)]. We applied canonical statistical mechanics to study the thermodynamics of ordering and in the most stable configuration we found the same concentration of Fe deficiencies in each layer along the c axis. We discuss the probabilities of the configurations and the averages of observables, such as lattice parameters and magnetic moments, as a function of temperature. At equilibrium, the Fe-deficient iron sulfide is expected to be fully ordered. The predicted electronic properties of the most stable configuration suggest that this material is antiferromagnetic. The simulated electronic structure shows that the most stable configuration of the Fe-deficient iron sulfide has semimetallic properties.

Original language	English
Pages (from-to)	7377-7386
Number of pages	10
Journal	Journal of Physical Chemistry C
Volume	129
Issue number	15
Early online date	4 Apr 2025
DOIs	https://doi.org/10.1021/acs.jpcc.4c05199
Publication status	Published - 17 Apr 2025

Bibliographical note

Publisher Copyright:
© 2025 The Authors. Published by American Chemical Society.

Funding

Via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/X035859/1), this work used the ARCHER2 UK National Supercomputing Service (https://www.archer2.ac.uk). We acknowledge the support from the Supercomputing Wales project, which is part-funded by the European Regional Development Fund (ERDF) via Welsh Government. This work was also undertaken on the ARC4 system of the High-Performance Computing facilities at the University of Leeds, United Kingdom. For the purpose of Open Access, the authors have applied for a CC BY public copyright licence to any Author Accepted Manuscript version arising from this submission.

Funders	Funder number
Engineering and Physical Sciences Research Council	EP/X035859/1
EPSRC
Supercomputing Wales project - European Regional Development Fund (ERDF) via Welsh Government

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abstract = "An Fe-deficient iron sulfide thin film with a nickeline (NiAs) type structure has been reported with a stoichiometry close to greigite (Fe3S4) [ Davis, E. M. ; Phys. Chem. Chem. Phys. 2019, 21, 20204-20210 ]. We have investigated the Fe-vacancy ordering in the nonstoichiometric iron sulfide with the NiAs-like structure using density functional theory calculations with a Hubbard Hamiltonian and long-range dispersion corrections [DFT + U - D3(BJ)]. We applied canonical statistical mechanics to study the thermodynamics of ordering and in the most stable configuration we found the same concentration of Fe deficiencies in each layer along the c axis. We discuss the probabilities of the configurations and the averages of observables, such as lattice parameters and magnetic moments, as a function of temperature. At equilibrium, the Fe-deficient iron sulfide is expected to be fully ordered. The predicted electronic properties of the most stable configuration suggest that this material is antiferromagnetic. The simulated electronic structure shows that the most stable configuration of the Fe-deficient iron sulfide has semimetallic properties.",

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N2 - An Fe-deficient iron sulfide thin film with a nickeline (NiAs) type structure has been reported with a stoichiometry close to greigite (Fe3S4) [ Davis, E. M. ; Phys. Chem. Chem. Phys. 2019, 21, 20204-20210 ]. We have investigated the Fe-vacancy ordering in the nonstoichiometric iron sulfide with the NiAs-like structure using density functional theory calculations with a Hubbard Hamiltonian and long-range dispersion corrections [DFT + U - D3(BJ)]. We applied canonical statistical mechanics to study the thermodynamics of ordering and in the most stable configuration we found the same concentration of Fe deficiencies in each layer along the c axis. We discuss the probabilities of the configurations and the averages of observables, such as lattice parameters and magnetic moments, as a function of temperature. At equilibrium, the Fe-deficient iron sulfide is expected to be fully ordered. The predicted electronic properties of the most stable configuration suggest that this material is antiferromagnetic. The simulated electronic structure shows that the most stable configuration of the Fe-deficient iron sulfide has semimetallic properties.

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Vacancy Ordering in Fe-Deficient Iron Sulfide with the NiAs-Type Structure

Abstract

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