Charge disproportionation and the pressure-induced insulator?metal transition in cubic perovskite PbCrO3

The perovskite PbCrO3 is an antiferromagnetic insulator. However, the fundamental interactions leading to the insulating state in this single-valent perovskite are unclear. Moreover, the origin of the unprecedented volume drop observed at a modest pressure of P = 1.6 GPa remains an outstanding problem. We report a variety of in situ pressure measurements including electron transport properties, X-ray absorption spectrum, and crystal structure study by X-ray and neutron diffraction. These studies reveal key information leading to the elucidation of the physics behind the insulating state and the pressure-induced transition. We argue that a charge disproportionation 3Cr4+ → 2Cr3+ + Cr6+ in association with the 6s-p hybridization on the Pb2+ is responsible for the insulating ground state of PbCrO3 at ambient pressure and the charge disproportionation phase is suppressed under pressure to give rise to a metallic phase at high pressure. The model is well supported by density function theory plus the correlation energy U (DFT+U) calculations.Fil: Cheng, Jinguang. University Of Texas At Austin; Estados Unidos. Chinese Academy Of Sciences; República de China. University of Tokyo. Institute for Solid State Physics; JapónFil: Kweon, K. E.. University Of Texas At Austin; Estados UnidosFil: Larregola, Sebastian Alberto. University Of Texas At Austin; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Investigaciones en Tecnología Química; ArgentinaFil: Ding, Yang. Argonne National Laboratory; Estados UnidosFil: Shirako, Y.. University Of Texas At Austin; Estados UnidosFil: Marshall, L. G.. University Of Texas At Austin; Estados Unidos. Northeastern University; Estados UnidosFil: Li, Z. Y.. University Of Texas At Austin; Estados UnidosFil: Li, X.. University Of Texas At Austin; Estados UnidosFil: Dos Santos, António M.. Oak Ridge National Laboratory. Quantum Condensed Matter Division; Estados UnidosFil: Suchomel, M. R.. Argonne National Laboratory; Estados UnidosFil: Matsubayashi, K.. University of Tokyo. Institute for Solid State Physics; JapónFil: Uwatoko, Y.. University of Tokyo. Institute for Solid State Physics; JapónFil: Hwang, G. S.. University Of Texas At Austin; Estados UnidosFil: Goodenough, John B.. University Of Texas At Austin; Estados UnidosFil: Zhou, J. S.. University Of Texas At Austin; Estados Unido