Stabilized Charge, Spin, and Orbital Ordering by the 6s2 Lone Pair in Bi0.5Pb0.5MnO3

Shogo Wakazaki; Takumi Nishikubo; Yuki Sakai; Kei Shigematsu; Hena Das; Depei Zhang; Qiang Zhang; Masaaki Matsuda; Masaki Azuma

doi:10.1021/acs.inorgchem.0c01748

Stabilized Charge, Spin, and Orbital Ordering by the 6s² Lone Pair in Bi_0.5Pb_0.5MnO₃

Inorg Chem. 2020 Sep 21;59(18):13390-13397. doi: 10.1021/acs.inorgchem.0c01748. Epub 2020 Sep 1.

Authors

Shogo Wakazaki¹, Takumi Nishikubo¹, Yuki Sakai^{1

2}, Kei Shigematsu^{1

2}, Hena Das^{1

3}, Depei Zhang⁴, Qiang Zhang⁴, Masaaki Matsuda⁴, Masaki Azuma^{1

2}

Affiliations

¹ Laboratory for Materials and Structures, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan.
² Kanagawa Institute of Industrial Science and Technology, 705-1 Shimoimaizumi, Ebina 243-0435, Japan.
³ World Research Hub Initiative, Institute for Innovative Research, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan.
⁴ Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States.

PMID: 32869627
DOI: 10.1021/acs.inorgchem.0c01748

Abstract

Bi and Pb ions with charge degree of freedom depending on 6s² and 6s⁰ electronic configurations were combined with the Mn ion in a perovskite oxide. Comprehensive theoretical and experimental investigations revealed the Bi³⁺_0.5Pb²⁺_0.5Mn³⁺_0.5Mn⁴⁺_0.5O₃ charge ordered state with CE-type spin and dz² orbital orderings as observed in La_0.5Ca_0.5MnO₃, Nd_0.5Sr_0.5MnO₃, and Bi_0.5Sr_0.5MnO₃. The charge and orbital orderings were preserved above 500 K owing to the stereochemical activity of Bi³⁺ and Pb²⁺ ions which stabilized the structural distortion.