The Impact of Structural Distortions on the Magnetism of Double Perovskites Containing 5d1 Transition-Metal Ions

da Cruz Pinha Barbosa, Victor; Xiong, Jie; Tran, Phuong Minh; McGuire, Michael A.; Yan, Jiaqiang; Warren, Matthew T.; Aguilar, Rolando Valdes; Zhang, Wenjuan; Randeria, Mohit; Trivedi, Nandini; Haskel, Daniel; Woodward, Patrick M.

doi:10.1021/acs.chemmater.1c03456

Title: The Impact of Structural Distortions on the Magnetism of Double Perovskites Containing 5d¹ Transition-Metal Ions

Journal Article · Wed Jan 19 00:00:00 EST 2022 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.1c03456· OSTI ID:1845763

da Cruz Pinha Barbosa, Victor ^[1]; Xiong, Jie ^[1]; Tran, Phuong Minh ^[1];

^[2];

^[2]; Warren, Matthew T. ^[1]; Aguilar, Rolando Valdes ^[1]; Zhang, Wenjuan ^[1]; Randeria, Mohit ^[1]; Trivedi, Nandini ^[1]; Haskel, Daniel ^[3];

^[1]

The Ohio State Univ., Columbus, OH (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

Five double perovskites, each containing a transition-metal ion with a 5d¹ configuration, have been studied to better understand the surprising diversity of magnetic ground states seen in these isoelectronic compounds. Ba₂ZnReO₆ adopts the cubic double perovskite structure and magnetically orders below 16 K, with a canted ferromagnetic structure and a saturated magnetization of ~0.24 μ_B/Re. X-ray magnetic circular dichroism indicates a substantial orbital moment of approximately 0.4 μ_B/Re that opposes the spin moment. The structures of Ba₂NaOsO₆ (canted ferromagnet, T_C = 7 K) and Ba₂LiOsO₆ (antiferromagnet, T_N = 8 K) are reinvestigated using time-of-flight neutron powder diffraction and found to crystallize with the cubic double perovskite structure. No evidence for a structural distortion can be found in either compound down to 10 K. Ba₂CdReO₆ is also cubic at room temperature but undergoes a structural transition upon cooling below ~180 K to a tetragonal structure with I4/m symmetry that involves compression of the Re–O bonds that are parallel to the c-axis. Sr₂LiOsO₆ shows a similar tetragonal distortion at room temperature and maintains that structure down to 10 K. Surprisingly, the Os-centered octahedron in Sr₂LiOsO₆ is distorted in the opposite direction, exhibiting an elongation of the Os–O bonds along the c-axis. Differences in the distortions of the octahedra lead to different magnetic ground states, antiferromagnetic (T_N = 4 K) for Ba₂CdReO₆ and spin glass (T_g = 30 K) for Sr₂LiOsO₆. Theoretical modeling shows that the varied magnetic behaviors of double perovskites containing 5d¹ ions are closely tied to crystallographic distortions. Furthermore, these distortions remove the degeneracy of the 5d t_2g orbitals, leading to changes in orbital occupation that ultimately determine which of the several competing magnetic ground states is favored.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). High Flux Isotope Reactor (HFIR); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Argonne National Lab. (ANL), Argonne, IL (United States)

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

Grant/Contract Number:: AC05-00OR22725; DMR-1420451; DMR-2011876; AC02-06CH11357

OSTI ID:: 1845763

Alternate ID(s):: OSTI ID: 1897899

Journal Information:: Chemistry of Materials, Vol. 34, Issue 3; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: The Impact of Structural Distortions on the Magnetism of Double Perovskites Containing 5d¹ Transition-Metal Ions