A Transition from Localized to Strongly Correlated Electron Behavior and Mixed Valence Driven by Physical or Chemical Pressure in ACo2As2 (A = Eu and Ca)

Tan, Xiaoyan; Fabbris, Gilberto; Haskel, Daniel; Yaroslavtsev, Alexander A.; Cao, Huibo; Thompson, Corey M.; Kovnir, Kirill; Menushenkov, Alexey P.; Chernikov, Roman V.; Garlea, V. Ovidiu; Shatruk, Michael

doi:10.1021/jacs.5b12659

Title: A Transition from Localized to Strongly Correlated Electron Behavior and Mixed Valence Driven by Physical or Chemical Pressure in ACo₂As₂ (A = Eu and Ca)

Journal Article · Wed Feb 03 00:00:00 EST 2016 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5b12659· OSTI ID:1335338

Tan, Xiaoyan ^[1]; Fabbris, Gilberto ^[2]; Haskel, Daniel ^[3]; Yaroslavtsev, Alexander A. ^[4]; Cao, Huibo ^[5]; Thompson, Corey M. ^[1]; Kovnir, Kirill ^[1]; Menushenkov, Alexey P. ^[6]; Chernikov, Roman V. ^[7]; Garlea, V. Ovidiu ^[5]; Shatruk, Michael ^[1]

Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source; Washington Univ., St. Louis, MO (United States). Dept. of Physics
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source
National Research Nuclear Univ. MEPhI (Moscow Engineering Physics Inst.), Moscow (Russian Federation); European X-ray Free-Electron Laser (XFEL), Hamburg (Germany)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Quantum Condensed Matter Division
National Research Nuclear Univ. MEPhI (Moscow Engineering Physics Inst.), Moscow (Russian Federation)
Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany). Photon Science

In this paper, we demonstrate that the action of physical pressure, chemical compression, or aliovalent substitution in ACo₂As₂ (A = Eu and Ca) has a general consequence of causing these antiferromagnetic materials to become ferromagnets. In all cases, the mixed valence triggered at the electropositive A site results in the increase of the Co 3d density of states at the Fermi level. Remarkably, the dramatic alteration of magnetic behavior results from the very minor (<0.15 electron) change in the population of the 3d orbitals. The mixed valence state of Eu observed in the high-pressure (HP) form of EuCo₂As₂ exhibits a remarkable stability, achieving the average oxidation state of +2.25 at 12.6 GPa. In the case of CaCo₂As₂, substituting even 10% of Eu or La into the Ca site causes ferromagnetic ordering of Co moments. Similar to HP-EuCo₂As₂, the itinerant 3d ferromagnetism emerges from electronic doping into the Co layer because of chemical compression of Eu sites in Ca_0.9Eu_0.1Co_1.91As₂ or direct electron doping in Ca_0.85La_0.15Co_1.89As₂. Finally, the results reported herein demonstrate the general possibility of amplifying minor localized electronic effects to achieve major changes in material’s properties via involvement of strongly correlated electrons.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Florida State Univ., Tallahassee, FL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Contributing Organization:: Washington Univ., St. Louis, MO (United States); National Research Nuclear Univ. MEPhI (Moscow Engineering Physics Inst.), Moscow (Russian Federation); European X-ray Free-Electron Laser (XFEL), Hamburg (Germany); Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)

Grant/Contract Number:: AC05-00OR22725; AC02-06CH11357; DMR-1507233

OSTI ID:: 1335338

Journal Information:: Journal of the American Chemical Society, Vol. 138, Issue 8; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: A Transition from Localized to Strongly Correlated Electron Behavior and Mixed Valence Driven by Physical or Chemical Pressure in ACo2As2 (A = Eu and Ca)

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