Collective Superexchange and Exchange Coupling Constants in the Hydrogenated Iron Oxide Particle Fe8O12H8

Gutsev, L. G.; Gutsev, G. L.; Jena, P.

doi:10.1021/acs.jpca.8b03034

Title: Collective Superexchange and Exchange Coupling Constants in the Hydrogenated Iron Oxide Particle Fe₈O₁₂H₈

Journal Article · Thu May 10 00:00:00 EDT 2018 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.8b03034· OSTI ID:1539172

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Virginia Commonwealth University, Richmond, VA (United States)
Florida A & M University, Tallahassee, FL (United States)

Motivated by the fact that Fe₂O₃ nanoparticles are used in the treatment of cancer, here we have examined the role of ligands on the magnetic properties of these particles by focusing on (Fe₂O₃)₄ as a prototype system with H as ligands. Using the Broken-Symmetry Density Functional Theory, we observed a strong collective superexchange in the hydrogenated Fe₈O₁₂H₈ cluster. The average antiferromagnetic exchange coupling constant between the four iron–iron oxo-bridged pairs was found to be -178 cm^–1, whereas coupling constants between hydroxo-bridged pairs were much smaller. We found that despite the apparent symmetry of the iron atom framework, it is not reasonable to assume this symmetry when fitting the exchange coupling constants. We also analyzed the geometrical and magnetic properties of Fe₈O₁₂H_n for n = 0–12 and found that hydrogenating oxo-bridges would generally inhibit the Fe–O–Fe antiferromagnetic superexchange interactions. Antiferromagnetic lowest total energy states become favorable only when specific distributions of hydrogen atoms are realized. The (HO)₄–Fe₄(all spin-up)–O₄–Fe₄(all spin-down)–(OH)₄ configuration in Fe₈O₁₂H₈ presents such an example. This symmetric configuration can be considered a superdiatomic system.

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Research Organization:: Virginia Commonwealth Univ., Richmond, VA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: FG02-96ER45579; AC02-05CH11231

OSTI ID:: 1539172

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 122, Issue 22; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 1 work

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Title: Collective Superexchange and Exchange Coupling Constants in the Hydrogenated Iron Oxide Particle Fe₈O₁₂H₈