Chemical design of electronic and magnetic energy scales of tetravalent praseodymium materials

Arun Ramanathan; Jensen Kaplan; Dumitru Claudiu Sergentu; Jacob A. Branson; Mykhaylo Ozerov; Alexander I. Kolesnikov; Stefan G. Minasian; Jochen Autschbach; John W. Freeland; Zhigang Jiang; Martin Mourigal; Henry S. La Pierre

doi:10.1038/s41467-023-38431-7

Chemical design of electronic and magnetic energy scales of tetravalent praseodymium materials

Arun Ramanathan, Jensen Kaplan, Dumitru Claudiu Sergentu, Jacob A. Branson, Mykhaylo Ozerov, Alexander I. Kolesnikov, Stefan G. Minasian, Jochen Autschbach, John W. Freeland, Zhigang Jiang, Martin Mourigal, Henry S. La Pierre

Direct Geometry

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19 Scopus citations

Abstract

Lanthanides in the trivalent oxidation state are typically described using an ionic picture that leads to localized magnetic moments. The hierarchical energy scales associated with trivalent lanthanides produce desirable properties for e.g., molecular magnetism, quantum materials, and quantum transduction. Here, we show that this traditional ionic paradigm breaks down for praseodymium in the tetravalent oxidation state. Synthetic, spectroscopic, and theoretical tools deployed on several solid-state Pr⁴⁺-oxides uncover the unusual participation of 4f orbitals in bonding and the anomalous hybridization of the 4f ¹ configuration with ligand valence electrons, analogous to transition metals. The competition between crystal-field and spin-orbit-coupling interactions fundamentally transforms the spin-orbital magnetism of Pr⁴⁺, which departs from the J _eff = 1/2 limit and resembles that of high-valent actinides. Our results show that Pr⁴⁺ ions are in a class on their own, where the hierarchy of single-ion energy scales can be tailored to explore new correlated phenomena in quantum materials.

Original language	English
Article number	3134
Journal	Nature Communications
Volume	14
Issue number	1
DOIs	https://doi.org/10.1038/s41467-023-38431-7
State	Published - Dec 2023

Funding

We are thankful to Dr. Harry Lane for his insightful discussions. The work of A.R. and H.S.L.P. at Georgia Tech was supported by the Beckman Foundation as part of a Beckman Young Investigator Award to H.S.L.P. The work of J.K. and M.M. at Georgia Tech was supported by the National Science Foundation through Grant No. NSF-DMR-1750186 awarded to M.M. The work of Z.J. at Georgia Tech was supported by the US Department of Energy through Grant No. DE-FG02-07ER46451 awarded to Z.J. Some of this work was performed in part at the Materials Characterization Facility at Georgia Tech, which is jointly supported by the GT Institute for Materials and the Institute for Electronics and Nanotechnology, and is a member of the National Nanotechnology Coordinated Infrastructure supported by the National Science Foundation under Grant No. ECCS-2025462. This research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract DE-AC02-06CH11357. The infrared measurements were performed at the National High Magnetic Field Laboratory, which is supported by the National Science Foundation Cooperative Agreement No. DMR-1644779 and the State of Florida. The work of D.-C.S. and J.A. at the University at Buffalo was supported by the US Department of Energy, Office of Basic Energy Sciences, Heavy Element Chemistry program, under grant DESC0001136 awarded to J.A. D.-C.S. and J.A. thank the Center for Computational Research (CCR) at the University at Buffalo for providing computational resources. D.-C.S. received research funding from the European Union’s Horizon 2020 Research and Innovation Program under Marie Sklodowska-Curie Grant Agreement No. 899546. D.-C.S. acknowledges infrastructure support provided through the RECENT AIR grant agreement MySMIS no. 127324. Work of J.A.B. and S.G.M at LBNL was supported by the Director, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences of the US Department of Energy (DOE) at LBNL under Contract No. DE-AC02-05CH11231. STXM research described in this paper was performed at the Canadian Light Source, which is supported by the Canada Foundation for Innovation, Natural Sciences and Engineering Research Council of Canada, the University of Saskatchewan, the Government of Saskatchewan, Western Economic Diversification Canada, the National Research Council Canada, and the Canadian Institutes of Health Research. We are thankful to Dr. Harry Lane for his insightful discussions. The work of A.R. and H.S.L.P. at Georgia Tech was supported by the Beckman Foundation as part of a Beckman Young Investigator Award to H.S.L.P. The work of J.K. and M.M. at Georgia Tech was supported by the National Science Foundation through Grant No. NSF-DMR-1750186 awarded to M.M. The work of Z.J. at Georgia Tech was supported by the US Department of Energy through Grant No. DE-FG02-07ER46451 awarded to Z.J. Some of this work was performed in part at the Materials Characterization Facility at Georgia Tech, which is jointly supported by the GT Institute for Materials and the Institute for Electronics and Nanotechnology, and is a member of the National Nanotechnology Coordinated Infrastructure supported by the National Science Foundation under Grant No. ECCS-2025462. This research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract DE-AC02-06CH11357. The infrared measurements were performed at the National High Magnetic Field Laboratory, which is supported by the National Science Foundation Cooperative Agreement No. DMR-1644779 and the State of Florida. The work of D.-C.S. and J.A. at the University at Buffalo was supported by the US Department of Energy, Office of Basic Energy Sciences, Heavy Element Chemistry program, under grant DESC0001136 awarded to J.A. D.-C.S. and J.A. thank the Center for Computational Research (CCR) at the University at Buffalo for providing computational resources. D.-C.S. received research funding from the European Union’s Horizon 2020 Research and Innovation Program under Marie Sklodowska-Curie Grant Agreement No. 899546. D.-C.S. acknowledges infrastructure support provided through the RECENT AIR grant agreement MySMIS no. 127324. Work of J.A.B. and S.G.M at LBNL was supported by the Director, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences of the US Department of Energy (DOE) at LBNL under Contract No. DE-AC02-05CH11231. STXM research described in this paper was performed at the Canadian Light Source, which is supported by the Canada Foundation for Innovation, Natural Sciences and Engineering Research Council of Canada, the University of Saskatchewan, the Government of Saskatchewan, Western Economic Diversification Canada, the National Research Council Canada, and the Canadian Institutes of Health Research.

Funders	Funder number
European Union’s Horizon 2020 Research and Innovation Program
GT Institute for Materials	ECCS-2025462
State of Florida	DESC0001136
National Science Foundation	NSF-DMR-1750186
U.S. Department of Energy	DE-FG02-07ER46451
Arnold and Mabel Beckman Foundation
Office of Science
Basic Energy Sciences	DMR-1644779, DE-AC02-06CH11357
Oak Ridge National Laboratory
Lawrence Berkeley National Laboratory	DE-AC02-05CH11231
University of Saskatchewan
Horizon 2020 Framework Programme	899546, 127324
Chemical Sciences, Geosciences, and Biosciences Division
Government of Saskatchewan
Canadian Institutes of Health Research
Natural Sciences and Engineering Research Council of Canada
Western Economic Diversification Canada
National Research Council Canada
Canada Foundation for Innovation

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10.1038/s41467-023-38431-7

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Ramanathan, A., Kaplan, J., Sergentu, D. C., Branson, J. A., Ozerov, M., Kolesnikov, A. I., Minasian, S. G., Autschbach, J., Freeland, J. W., Jiang, Z., Mourigal, M., & La Pierre, H. S. (2023). Chemical design of electronic and magnetic energy scales of tetravalent praseodymium materials. Nature Communications, 14(1), Article 3134. https://doi.org/10.1038/s41467-023-38431-7

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abstract = "Lanthanides in the trivalent oxidation state are typically described using an ionic picture that leads to localized magnetic moments. The hierarchical energy scales associated with trivalent lanthanides produce desirable properties for e.g., molecular magnetism, quantum materials, and quantum transduction. Here, we show that this traditional ionic paradigm breaks down for praseodymium in the tetravalent oxidation state. Synthetic, spectroscopic, and theoretical tools deployed on several solid-state Pr4+-oxides uncover the unusual participation of 4f orbitals in bonding and the anomalous hybridization of the 4f 1 configuration with ligand valence electrons, analogous to transition metals. The competition between crystal-field and spin-orbit-coupling interactions fundamentally transforms the spin-orbital magnetism of Pr4+, which departs from the J eff = 1/2 limit and resembles that of high-valent actinides. Our results show that Pr4+ ions are in a class on their own, where the hierarchy of single-ion energy scales can be tailored to explore new correlated phenomena in quantum materials.",

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AU - Ozerov, Mykhaylo

AU - Kolesnikov, Alexander I.

AU - Minasian, Stefan G.

AU - Autschbach, Jochen

AU - Freeland, John W.

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AU - Mourigal, Martin

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N2 - Lanthanides in the trivalent oxidation state are typically described using an ionic picture that leads to localized magnetic moments. The hierarchical energy scales associated with trivalent lanthanides produce desirable properties for e.g., molecular magnetism, quantum materials, and quantum transduction. Here, we show that this traditional ionic paradigm breaks down for praseodymium in the tetravalent oxidation state. Synthetic, spectroscopic, and theoretical tools deployed on several solid-state Pr4+-oxides uncover the unusual participation of 4f orbitals in bonding and the anomalous hybridization of the 4f 1 configuration with ligand valence electrons, analogous to transition metals. The competition between crystal-field and spin-orbit-coupling interactions fundamentally transforms the spin-orbital magnetism of Pr4+, which departs from the J eff = 1/2 limit and resembles that of high-valent actinides. Our results show that Pr4+ ions are in a class on their own, where the hierarchy of single-ion energy scales can be tailored to explore new correlated phenomena in quantum materials.

AB - Lanthanides in the trivalent oxidation state are typically described using an ionic picture that leads to localized magnetic moments. The hierarchical energy scales associated with trivalent lanthanides produce desirable properties for e.g., molecular magnetism, quantum materials, and quantum transduction. Here, we show that this traditional ionic paradigm breaks down for praseodymium in the tetravalent oxidation state. Synthetic, spectroscopic, and theoretical tools deployed on several solid-state Pr4+-oxides uncover the unusual participation of 4f orbitals in bonding and the anomalous hybridization of the 4f 1 configuration with ligand valence electrons, analogous to transition metals. The competition between crystal-field and spin-orbit-coupling interactions fundamentally transforms the spin-orbital magnetism of Pr4+, which departs from the J eff = 1/2 limit and resembles that of high-valent actinides. Our results show that Pr4+ ions are in a class on their own, where the hierarchy of single-ion energy scales can be tailored to explore new correlated phenomena in quantum materials.

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Chemical design of electronic and magnetic energy scales of tetravalent praseodymium materials

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