Valence skipping, internal doping and site-selective Mott transition in PbCoO${}_3$ under pressure

Abstract

We present a computational study of PbCoO${}_3$ at ambient and elevated pressure. We employ the static and dynamic treatment of local correlation in form of density functional theory + $U$ (DFT+$U$) and + dynamical mean-field theory (DFT+DMFT). Our results capture the experimentally observed crystal structures and identify the unsaturated Pb $6s$ - O $2p$ bonds as the driving force beyond the complex physics of PbCoO${}_3$. We provide a geometrical analysis of the structural distortions and we discuss their implications, in particular, the internal doping, which triggers transition between phases with and without local moments and a site selective Mott transition in the low-pressure phase.

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Cited by in corpus (2)

• Metal-insulator transition and local-moment collapse in negative charge-transfer CaFeO${}_3$ under pressure
• Mechanism of intermetallic charge transfer and bond disproportionation in BiNiO${}_3$ and PbNiO${}_3$ revealed by hard x-ray photoemission spectroscopy