Density Functional Theory Study of Iron–Oxygen Divacancies in Magnetite (Fe3O4) and Hematite (Fe2O3)

Srivastava, Shivani; Uberuaga, Blas Pedro; Asta, Mark

doi:10.1021/acs.jpcc.5c02852

Density Functional Theory Study of Iron–Oxygen Divacancies in Magnetite (Fe₃O₄) and Hematite (Fe₂O₃)

Journal Article · Mon Aug 18 00:00:00 EDT 2025 · The Journal of Physical Chemistry C

DOI:https://doi.org/10.1021/acs.jpcc.5c02852· OSTI ID:2589849

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University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Density functional theory (DFT) calculations are employed to investigate the formation energies, charge redistribution, and binding energies of iron–oxygen divacancies in magnetite (Fe₃O₄) and hematite (Fe₂O₃). For magnetite, we focus on the low-temperature phase to explore variations with local environments. Building on previous DFT calculations of the variations in formation energies for oxygen vacancies with local charge and spin order in magnetite, we extend this analysis to include octahedral iron vacancies before analyzing the iron–oxygen divacancies. We also assessed the relative stability of iron–oxygen divacancies by comparing their formation energies with those of individual vacancies. Our findings reveal a significant energetic driving force for the formation of divacancy clusters, particularly in magnetite, where divacancies in the +1 charge state exhibit formation energies comparable to those of neutral iron vacancies under oxidizing conditions. In hematite, the results indicate a strong tendency for oxygen vacancies to bind to iron vacancies. These results highlight the significance of iron–oxygen vacancy complexes in the transport properties of iron oxides, with particular relevance to diffusion mechanisms under irradiation conditions.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: 89233218CNA000001; AC02-05CH11231

OSTI ID:: 2589849

Report Number(s):: LA-UR--25-23978; 10.1021/acs.jpcc.5c02852; 1932-7455

Journal Information:: The Journal of Physical Chemistry C, Journal Name: The Journal of Physical Chemistry C Journal Issue: 35 Vol. 129; ISSN 1932-7455; ISSN 1932-7447

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Density Functional Theory Study of Iron–Oxygen Divacancies in Magnetite (Fe3O4) and Hematite (Fe2O3)

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