DOE OSTI2025
As a recently identified Mott system, PbCrO 3 remains largely unexplored, especially for its band structure, leading to many contentious issues on its structural, electronic, and magnetic properties. Here we present a comprehensive study of two different Pb 1−𝛿 CrO 3 (δ = 0 and 0.15) samples involving atomic deficiency prepared under pressure. By means of state-of-the-art diffraction techniques, the crystal structure of PbCrO 3 is definitively determined to adopt the pristine 𝑃𝑚$\overline{3}$𝑚 symmetry, rather than other previously misassigned structures of M2-Pm$\overline{3}$𝑚 and Pmnm. The two materials exhibit a similar charge-transfer-type insulating band structure, and the charge-transfer effect splits both Cr 2𝑝 and Pb 4𝑓 orbitals, rationalizing doublet splitting of the associated spectral lines. Nearly identical nominal cationic valence states of Cr 4+ and Pb 2+ are identified for this oxide system, hence calling into question the validity of recently proposed charge disproportionation mechanisms. In addition, Pb 0.85 CrO 3 exhibits an anomalously higher Néel temperature of ∼240 K than that of PbCrO 3 (i.e., ∼200 K), likely due to the deficiency-induced enhancements of Cr3𝑑–O2𝑝 orbital overlap and magnetic exchange. In conclusion, these findings provide much solid evidence to look into the fundamental properties of this important material system.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗