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Charge disproportionation of mixed-valent Cr triggered by Bi lone-pair effect in the A-site-ordered perovskite BiCu3Cr4O12

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Isobe,  M.
Scientific Facility Crystal Growth (Masahiko Isobe), Max Planck Institute for Solid State Research, Max Planck Society;
Department Quantum Materials (Hidenori Takagi), Max Planck Institute for Solid State Research, Max Planck Society;

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Yaresko,  A.
Department Quantum Materials (Hidenori Takagi), Max Planck Institute for Solid State Research, Max Planck Society;
Department Solid State Spectroscopy (Bernhard Keimer), Max Planck Institute for Solid State Research, Max Planck Society;

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Dinnebier,  R. E.
Scientific Facility X-Ray Diffraction (Robert E. Dinnebier), Max Planck Institute for Solid State Research, Max Planck Society;

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Takagi,  H.
Department Quantum Materials (Hidenori Takagi), Max Planck Institute for Solid State Research, Max Planck Society;

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Citation

Etter, M., Isobe, M., Sakurai, H., Yaresko, A., Dinnebier, R. E., & Takagi, H. (2018). Charge disproportionation of mixed-valent Cr triggered by Bi lone-pair effect in the A-site-ordered perovskite BiCu3Cr4O12. Physical Review B, 97(19): 195111.


Cite as: https://hdl.handle.net/21.11116/0000-000E-D616-8
Abstract
A new A-site-ordered perovskite BiCu3Cr4O12 is synthesized under a high pressure of 7.7 GPa. A phase transition from a paramagnetic metal to a ferrimagnetic metal is observed at T-c = 190K accompanied with a structural change from cubic to monoclinic. Structural analysis of the low-temperature monoclinic phase reveals that this transition represents a charge disproportionation of Cr3.75+ into Cr4+ and Cr3.5+. We argue that the asymmetric displacement of Bi caused by a lone-pair effect triggers the formation of a dimeric Cr4+ O-2(5) unit and leads to an ordering of Cr4+ and Cr3.5+ below the transition.