A family of rare earth molybdenum bronzes: Oxides consisting of periodic arrays of interacting magnetic units

Schneemeyer, L. F.; Siegrist, T.; Besara, T.; Lundberg, M.; Sun, J.; Singh, D. J.

doi:10.1016/j.jssc.2015.03.028

Title: A family of rare earth molybdenum bronzes: Oxides consisting of periodic arrays of interacting magnetic units

Journal Article · Mon Apr 06 00:00:00 EDT 2015 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2015.03.028· OSTI ID:1333511

Schneemeyer, L. F. ^[1];

^[2]; Besara, T. ^[3]; Lundberg, M. ^[2]; Sun, J. ^[4]; Singh, D. J. ^[5]

Montclair State Univ., Montclair, NJ (United States)
FAMU-FSU College of Engineering, Tallahassee, FL (United States); National High Magnetic Field Lab., Tallahassee, FL (United States)
National High Magnetic Field Lab., Tallahassee, FL (United States)
FAMU-FSU College of Engineering, Tallahassee, FL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Here we carried out a detailed structural study of the family of rare earth molybdenum bronzes, and synthesized reduced ternary molybdates of composition LnMo₁₆O₄₄. Bond valence sum (BVS) calculations clearly show that the molybdenum ions in tetrahedral coordination are hexavalent while the electron count in the primitive unit cell is odd. Yet, measurements show that the phases are semiconductors. The temperature dependence of the magnetic susceptibility of samples containing several different rare earth elements was measured. These measurements verified the presence of a 6.5 K magnetic phase transition not arising from the rare earth constituent, but likely associated with the unique isolated ReO₃-type Mo₈O₃₆ structural subunits in this phase. To better understand the behavior of these materials, electronic structure calculations were performed within density functional theory. Results suggest a magnetic state in which these structural moieties have an internal ferromagnetic arrangement, with small ~1/8 μ_B moments on each Mo. We suggest that the Mo₈O₃₆ units behave like pseudoatoms with spin 1/2 derived from a single hole distributed over the eight Mo atoms that are strongly hybridized with the O atoms of the subunit. Interestingly, while the compound is antiferromagnetic, our calculations suggest that a field-stabilized ferromagnetic state, if achievable, will be a narrow band half-metal.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Contributing Organization:: Oak Ridge National Laboratory; Montclair State University

Grant/Contract Number:: SC0008832; AC05-00OR22725

OSTI ID:: 1333511

Alternate ID(s):: OSTI ID: 1253042; OSTI ID: 1265478

Journal Information:: Journal of Solid State Chemistry, Vol. 227, Issue C; ISSN 0022-4596

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 2 works

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References (28)

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CSD 1410864: Experimental Crystal Structure Determination: Non-CSD Structure Schneemeyer, L. F.; Siegrist, T.; Besara, T. https://doi.org/10.25505/fiz.icsd.cc1jc3rr The current record is supplemented by this dataset	dataset	May 2015
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Title: A family of rare earth molybdenum bronzes: Oxides consisting of periodic arrays of interacting magnetic units

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