Competing Magnetic Interactions and the Role of Unpaired 4f Electrons in Oxygen-Deficient Perovskites Ba3RFe2O7.5 (R = Y, Dy)

Alex J. Brown; Maxim Avdeev; Alicia Manjón-Sanz; Helen E.A. Brand; Chris D. Ling

doi:10.1021/acs.inorgchem.3c00524

Competing Magnetic Interactions and the Role of Unpaired 4f Electrons in Oxygen-Deficient Perovskites Ba₃RFe₂O_7.5 (R = Y, Dy)

Alex J. Brown, Maxim Avdeev, Alicia Manjón-Sanz, Helen E.A. Brand, Chris D. Ling

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Abstract

Oxygen-deficient perovskite compounds with the general formula Ba₃RFe₂O_7.5 present a good opportunity to study competing magnetic interactions between Fe³⁺ 3d cations with and without the involvement of unpaired 4f electrons on R³⁺ cations. From analysis of neutron powder diffraction data, complemented by ab initio density functional theory calculations, we determined the magnetic ground states when R³⁺ = Y³⁺ (non-magnetic) and Dy³⁺ (4f⁹). They both adopt complex long-range ordered antiferromagnetic structures below T_N = 6.6 and 14.5 K, respectively, with the same magnetic space group C_a2/c (BNS #15.91). However, the dominant influence of f-electron magnetism is clear in temperature dependence and differences between the size of the ordered moments on the two crystallographically independent Fe sites, one of which is enhanced by R-O-Fe superexchange in the Dy compound, while the other is frustrated by it.

Original language	English
Pages (from-to)	6786-6793
Number of pages	8
Journal	Inorganic Chemistry
Volume	62
Issue number	17
DOIs	https://doi.org/10.1021/acs.inorgchem.3c00524
State	Published - May 1 2023

Funding

This work was supported by the Australian Government Research Training Stipend and the Australian Research Council – Discovery Projects scheme (DP200100959). This work was supported by the Australian Government Research Training Stipend. We thank ANSTO for beamtime awarded on the Australian Synchrotron PD and ACNS Echidna beamlines and Oak Ridge National Laboratory for beamtime awarded on the SNS POWGEN beamline. Preliminary XRD data were collected at Sydney Analytical, a Core Research Facility at the University of Sydney. This manuscript has been co-authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan. This work was supported by the Australian Government Research Training Stipend. We thank ANSTO for beamtime awarded on the Australian Synchrotron PD and ACNS Echidna beamlines and Oak Ridge National Laboratory for beamtime awarded on the SNS POWGEN beamline. Preliminary XRD data were collected at Sydney Analytical, a Core Research Facility at the University of Sydney. This manuscript has been co-authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan. This work was supported by the Australian Government Research Training Stipend and the Australian Research Council - Discovery Projects scheme (DP200100959).

Funders	Funder number
U.S. Department of Energy
Australian Research Council	DP200100959
University of Sydney	DE-AC05-00OR22725

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title = "Competing Magnetic Interactions and the Role of Unpaired 4f Electrons in Oxygen-Deficient Perovskites Ba3RFe2O7.5 (R = Y, Dy)",

abstract = "Oxygen-deficient perovskite compounds with the general formula Ba3RFe2O7.5 present a good opportunity to study competing magnetic interactions between Fe3+ 3d cations with and without the involvement of unpaired 4f electrons on R3+ cations. From analysis of neutron powder diffraction data, complemented by ab initio density functional theory calculations, we determined the magnetic ground states when R3+ = Y3+ (non-magnetic) and Dy3+ (4f9). They both adopt complex long-range ordered antiferromagnetic structures below TN = 6.6 and 14.5 K, respectively, with the same magnetic space group Ca2/c (BNS #15.91). However, the dominant influence of f-electron magnetism is clear in temperature dependence and differences between the size of the ordered moments on the two crystallographically independent Fe sites, one of which is enhanced by R-O-Fe superexchange in the Dy compound, while the other is frustrated by it.",

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N2 - Oxygen-deficient perovskite compounds with the general formula Ba3RFe2O7.5 present a good opportunity to study competing magnetic interactions between Fe3+ 3d cations with and without the involvement of unpaired 4f electrons on R3+ cations. From analysis of neutron powder diffraction data, complemented by ab initio density functional theory calculations, we determined the magnetic ground states when R3+ = Y3+ (non-magnetic) and Dy3+ (4f9). They both adopt complex long-range ordered antiferromagnetic structures below TN = 6.6 and 14.5 K, respectively, with the same magnetic space group Ca2/c (BNS #15.91). However, the dominant influence of f-electron magnetism is clear in temperature dependence and differences between the size of the ordered moments on the two crystallographically independent Fe sites, one of which is enhanced by R-O-Fe superexchange in the Dy compound, while the other is frustrated by it.

AB - Oxygen-deficient perovskite compounds with the general formula Ba3RFe2O7.5 present a good opportunity to study competing magnetic interactions between Fe3+ 3d cations with and without the involvement of unpaired 4f electrons on R3+ cations. From analysis of neutron powder diffraction data, complemented by ab initio density functional theory calculations, we determined the magnetic ground states when R3+ = Y3+ (non-magnetic) and Dy3+ (4f9). They both adopt complex long-range ordered antiferromagnetic structures below TN = 6.6 and 14.5 K, respectively, with the same magnetic space group Ca2/c (BNS #15.91). However, the dominant influence of f-electron magnetism is clear in temperature dependence and differences between the size of the ordered moments on the two crystallographically independent Fe sites, one of which is enhanced by R-O-Fe superexchange in the Dy compound, while the other is frustrated by it.

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Competing Magnetic Interactions and the Role of Unpaired 4f Electrons in Oxygen-Deficient Perovskites Ba₃RFe₂O_7.5 (R = Y, Dy)

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