Large Positive Zero-Field Splitting in the Cluster Magnet Ba3CeRu2O9

Qiang Chen; Shiyu Fan; Keith M. Taddei; Matthew B. Stone; Alexander I. Kolesnikov; Jinguang Cheng; Janice L. Musfeldt; Haidong Zhou; Adam A. Aczel

doi:10.1021/jacs.9b03389

Large Positive Zero-Field Splitting in the Cluster Magnet Ba₃CeRu₂O₉

Qiang Chen, Shiyu Fan, Keith M. Taddei, Matthew B. Stone, Alexander I. Kolesnikov, Jinguang Cheng, Janice L. Musfeldt, Haidong Zhou, Adam A. Aczel

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

13 Scopus citations

Abstract

We present the synthesis and magnetic characterization of a polycrystalline sample of the 6H-perovskite Ba₃CeRu₂O₉, which consists of Ru dimers based on face-sharing RuO₆ octahedra. Our low-temperature magnetic susceptibility, magnetization, and neutron powder diffraction results reveal a nonmagnetic singlet ground state for the dimers. Inelastic neutron scattering, infrared spectroscopy, and the magnetic susceptibility over a wide temperature range are best explained by a molecular orbital model with a zero-field splitting parameter D = 85 meV for the S_tot = 1 electronic ground-state multiplet. This large value is likely due to strong mixing between this ground-state multiplet and low-lying excited multiplets, arising from a sizable spin molecular orbital coupling combined with an axial distortion of the Ru₂O₉ units. Although the positive sign for the splitting ensures that Ba₃CeRu₂O₉ is not a single molecule magnet, our work suggests that the search for these interesting materials should be extended beyond Ba₃CeRu₂O₉ to other molecular magnets based on metal-metal bonding.

Original language	English
Pages (from-to)	9928-9936
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	141
Issue number	25
DOIs	https://doi.org/10.1021/jacs.9b03389
State	Published - Jun 26 2019

Funding

We appreciate useful discussions with S. A. J. Kimber and C. Eichstaedt. Research at the University of Tennessee is supported by the National Science Foundation, Division of Materials Research, under award NSF-DMR 1350002 (HDZ) and the Department of Energy, Office of Basic Energy Sciences, Materials Science Division, under award DE-FG02-01ER45885 (J.L.M.). J.C. is supported by the MOST, NSFC, and CAS through projects with Grant nos. 2018YFA0305700, 11874400, and QYZDB-SSW-SLH013. A portion of this research used resources at the High Flux Isotope Reactor and the Spallation Neutron Source, which are DOE Office of Science User Facilities operated by Oak Ridge National Laboratory.

Funders	Funder number
Materials Science Division	DE-FG02-01ER45885
Office of Basic Energy Sciences
National Science Foundation
U.S. Department of Energy
Division of Materials Research	NSF-DMR 1350002
University of Tennessee
College of Arts and Sciences, University of Nebraska-Lincoln	QYZDB-SSW-SLH013, 2018YFA0305700, 11874400
National Natural Science Foundation of China
Ministry of Science and Technology

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title = "Large Positive Zero-Field Splitting in the Cluster Magnet Ba3CeRu2O9",

abstract = "We present the synthesis and magnetic characterization of a polycrystalline sample of the 6H-perovskite Ba3CeRu2O9, which consists of Ru dimers based on face-sharing RuO6 octahedra. Our low-temperature magnetic susceptibility, magnetization, and neutron powder diffraction results reveal a nonmagnetic singlet ground state for the dimers. Inelastic neutron scattering, infrared spectroscopy, and the magnetic susceptibility over a wide temperature range are best explained by a molecular orbital model with a zero-field splitting parameter D = 85 meV for the Stot = 1 electronic ground-state multiplet. This large value is likely due to strong mixing between this ground-state multiplet and low-lying excited multiplets, arising from a sizable spin molecular orbital coupling combined with an axial distortion of the Ru2O9 units. Although the positive sign for the splitting ensures that Ba3CeRu2O9 is not a single molecule magnet, our work suggests that the search for these interesting materials should be extended beyond Ba3CeRu2O9 to other molecular magnets based on metal-metal bonding.",

author = "Qiang Chen and Shiyu Fan and Taddei, {Keith M.} and Stone, {Matthew B.} and Kolesnikov, {Alexander I.} and Jinguang Cheng and Musfeldt, {Janice L.} and Haidong Zhou and Aczel, {Adam A.}",

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year = "2019",

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doi = "10.1021/jacs.9b03389",

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AU - Chen, Qiang

AU - Fan, Shiyu

AU - Taddei, Keith M.

AU - Stone, Matthew B.

AU - Kolesnikov, Alexander I.

AU - Cheng, Jinguang

AU - Musfeldt, Janice L.

AU - Zhou, Haidong

AU - Aczel, Adam A.

PY - 2019/6/26

Y1 - 2019/6/26

N2 - We present the synthesis and magnetic characterization of a polycrystalline sample of the 6H-perovskite Ba3CeRu2O9, which consists of Ru dimers based on face-sharing RuO6 octahedra. Our low-temperature magnetic susceptibility, magnetization, and neutron powder diffraction results reveal a nonmagnetic singlet ground state for the dimers. Inelastic neutron scattering, infrared spectroscopy, and the magnetic susceptibility over a wide temperature range are best explained by a molecular orbital model with a zero-field splitting parameter D = 85 meV for the Stot = 1 electronic ground-state multiplet. This large value is likely due to strong mixing between this ground-state multiplet and low-lying excited multiplets, arising from a sizable spin molecular orbital coupling combined with an axial distortion of the Ru2O9 units. Although the positive sign for the splitting ensures that Ba3CeRu2O9 is not a single molecule magnet, our work suggests that the search for these interesting materials should be extended beyond Ba3CeRu2O9 to other molecular magnets based on metal-metal bonding.

AB - We present the synthesis and magnetic characterization of a polycrystalline sample of the 6H-perovskite Ba3CeRu2O9, which consists of Ru dimers based on face-sharing RuO6 octahedra. Our low-temperature magnetic susceptibility, magnetization, and neutron powder diffraction results reveal a nonmagnetic singlet ground state for the dimers. Inelastic neutron scattering, infrared spectroscopy, and the magnetic susceptibility over a wide temperature range are best explained by a molecular orbital model with a zero-field splitting parameter D = 85 meV for the Stot = 1 electronic ground-state multiplet. This large value is likely due to strong mixing between this ground-state multiplet and low-lying excited multiplets, arising from a sizable spin molecular orbital coupling combined with an axial distortion of the Ru2O9 units. Although the positive sign for the splitting ensures that Ba3CeRu2O9 is not a single molecule magnet, our work suggests that the search for these interesting materials should be extended beyond Ba3CeRu2O9 to other molecular magnets based on metal-metal bonding.

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Large Positive Zero-Field Splitting in the Cluster Magnet Ba₃CeRu₂O₉

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