Kanagawa Academy of Science and Technology , KSP, 3-2-1 Sakado, Takatsu-ku, Kawasaki City, Kanagawa 213-0012, Japan.
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences , Beijing 100190, China.
J Am Chem Soc. 2017 Mar 29;139(12):4574-4581. doi: 10.1021/jacs.7b01851. Epub 2017 Mar 15.
Perovskite PbCoO synthesized at 12 GPa was found to have an unusual charge distribution of PbPbCoCoO with charge orderings in both the A and B sites of perovskite ABO. Comprehensive studies using density functional theory (DFT) calculation, electron diffraction (ED), synchrotron X-ray diffraction (SXRD), neutron powder diffraction (NPD), hard X-ray photoemission spectroscopy (HAXPES), soft X-ray absorption spectroscopy (XAS), and measurements of specific heat as well as magnetic and electrical properties provide evidence of lead ion and cobalt ion charge ordering leading to PbPbCoCoO quadruple perovskite structure. It is shown that the average valence distribution of PbCoO between PbCrO and PbNiO can be stabilized by tuning the energy levels of Pb 6s and transition metal 3d orbitals.
在 12 GPa 下合成的钙钛矿 PbCoO 被发现具有不寻常的 PbPbCoCoO 电荷分布，其中钙钛矿 ABO 的 A 和 B 位都存在电荷有序。使用密度泛函理论 (DFT) 计算、电子衍射 (ED)、同步加速器 X 射线衍射 (SXRD)、中子粉末衍射 (NPD)、硬 X 射线光电子能谱 (HAXPES)、软 X 射线吸收光谱 (XAS) 以及比热、磁性和电性能的综合研究提供了 Pb 离子和 Co 离子电荷有序导致 PbPbCoCoO 四重钙钛矿结构的证据。结果表明，通过调整 Pb 6s 和过渡金属 3d 轨道的能级，可以稳定 PbCoO 中 PbCrO 和 PbNiO 之间的平均价态分布。
