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

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

doi:10.1038/s41467-023-38431-7

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

Journal Article · Tue May 30 00:00:00 EDT 2023 · Nature Communications

DOI:https://doi.org/10.1038/s41467-023-38431-7· OSTI ID:1976001

Ramanathan, Arun ^[1]; Kaplan, Jensen ^[1]; Sergentu, Dumitru-Claudiu ^[2]; ^[3]; Ozerov, Mykhaylo ^[4]; ^[5]; Minasian, Stefan G. ^[6]; Autschbach, Jochen ^[7]; Freeland, John ^[8]; Jiang, Zhigang ^[1]; Mourigal, Martin ^[1]; La Pierre, Henry S. ^[1]

Georgia Institute of Technology, Atlanta, GA (United States)
Univ. of Rennes (France); Alexandru Ioan Cuza University of Iaşi (Romania); State Univ. of New York (SUNY), Buffalo, NY (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Florida State Univ., Tallahassee, FL (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
State Univ. of New York (SUNY), Buffalo, NY (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

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 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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; AC05-00OR22725; FG02-07ER46451; SC0001136

OSTI ID:: 1976001

Alternate ID(s):: OSTI ID: 2371036

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 14; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Raw output data for "Chemical design of electronic and magnetic energy scales of tetravalent praseodymium materials", DOI: 10.1038/s41467-023-38431-7 Ramanathan, Arun; Kaplan, Jensen; Sergentu, Dumitru-Claudiu Zenodo https://doi.org/10.5281/zenodo.7932208	dataset	January 2023
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