Stabilized Charge, Spin, and Orbital Ordering by the 6s(2) Lone Pair in Bi0.5Pb0.5MnO3

Wakazaki S; Nishikubo T; Sakai Y; Shigematsu K; Das H; Zhang DP; Zhang Q; Matsuda M; Azuma M

Inorganic Chemistry, Vol.59, No.18, 13390-13397, 2020

DOI10.1021/acs.inorgchem.0c01748 Export Citation

Stabilized Charge, Spin, and Orbital Ordering by the 6s(2) Lone Pair in Bi0.5Pb0.5MnO3

Wakazaki S, Nishikubo T, Sakai Y, Shigematsu K, Das H, Zhang DP, Zhang Q, Matsuda M, Azuma M

Bi and Pb ions with charge degree of freedom depending on 6s(2) and 6s(0) electronic configurations were combined with the Mn ion in a perovskite oxide. Comprehensive theoretical and experimental investigations revealed the Bi0.53+Pb2+ Mn-0.5(3+) 0.5Mn4+O3 charge ordered state with CE-type spin and dz(2) orbital orderings as observed in La0.5Ca0.5MnO3, Nd0.5Sr0.5MnO3, and Bi0.5Sr0.5MnO3. 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.