Crystal-chemical anomalies in nonsuperconducting PrBa2Cu3O7

Studies of the crystal chemistry of nonsuperconducting PrBa₂Cu₃O₇ indicate that this compound is strictly isostructural with its superconducting RBa₂Cu₃O₇ (R = Y, rare earth) analogs. Crystallographically, Pr is present in the trivalent state according to the structural trends exhibited by the RBa₂Cu₃O₇ series as a function of R³⁺ ionic radius. The sole structural anomaly attributable to the presence of Pr³⁺ in the YBa₂Cu₃O₇ structure is a next-next-nearest neighbor effect and consists of an unusually short axial Cu-O distance, i.e., a short bond length between the in-plane copper and the chain oxygen. The correlation of this anomaly with the nonmetallic/nonsuperconducting properties of PrBa₂Cu₃O₇ supports a variety of literature reports, both theoretical and experimental, suggesting that the apical oxygen in the YBa₂Cu₃O₇ structure plays a critical role in mediating the appearance of superconductivity. The mechanism by which the f-electrons in Pr³⁺ (f ²) interact with the Cu-O manifold to produce the nonmetallic behavior of PrBa₂Cu₃O₇ remains unknown; however, superconductivity is “turned back on” for Nd³⁺ (f ³), immediately next to Pr and just slightly smaller. Careful comparative studies of superconducting NdBa₂Cu₃O₇ and nonmetallic PrBa₂Cu₃O₇ are needed to elucidate the critical difference in the behavior of the f-electrons and may shed light on the fundamental mechanism of high-temperature superconductivity in copper oxides.