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

Author

Listed:
  • Arun Ramanathan

    (Georgia Institute of Technology)

  • Jensen Kaplan

    (Georgia Institute of Technology)

  • Dumitru-Claudiu Sergentu

    (University of Rennes, CNRS ISCR (Institut des Sciences Chimiques de Rennes) - UMR 6226
    A. I. Cuza University of Iași, RA-03 Laboratory (RECENT AIR)
    University at Buffalo, State University of New York)

  • Jacob A. Branson

    (University of California
    Lawrence Berkeley National Laboratory)

  • Mykhaylo Ozerov

    (Florida State University)

  • Alexander I. Kolesnikov

    (Oak Ridge National Laboratory)

  • Stefan G. Minasian

    (Lawrence Berkeley National Laboratory)

  • Jochen Autschbach

    (University at Buffalo, State University of New York)

  • John W. Freeland

    (Argonne National Laboratory)

  • Zhigang Jiang

    (Georgia Institute of Technology)

  • Martin Mourigal

    (Georgia Institute of Technology)

  • Henry S. La Pierre

    (Georgia Institute of Technology
    Georgia Institute of Technology)

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 4f1 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 Jeff = 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.

Suggested Citation

  • 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 & , 2023. "Chemical design of electronic and magnetic energy scales of tetravalent praseodymium materials," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-38431-7
    DOI: 10.1038/s41467-023-38431-7
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    References listed on IDEAS

    as
    1. J. H. Shim & K. Haule & G. Kotliar, 2007. "Fluctuating valence in a correlated solid and the anomalous properties of δ-plutonium," Nature, Nature, vol. 446(7135), pages 513-516, March.
    2. David M. King & Peter A. Cleaves & Ashley J. Wooles & Benedict M. Gardner & Nicholas F. Chilton & Floriana Tuna & William Lewis & Eric J. L. McInnes & Stephen T. Liddle, 2016. "Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes," Nature Communications, Nature, vol. 7(1), pages 1-14, December.
    3. Vipul Chaturvedi & Supriya Ghosh & Dominique Gautreau & William M. Postiglione & John E. Dewey & Patrick Quarterman & Purnima P. Balakrishnan & Brian J. Kirby & Hua Zhou & Huikai Cheng & Amanda Huon &, 2022. "Room-temperature valence transition in a strain-tuned perovskite oxide," Nature Communications, Nature, vol. 13(1), pages 1-12, December.
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