Abstract
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+ (f2) interact with the Cu-O manifold to produce the nonmetallic behavior of PrBa2Cu3O7 remains unknown; however, superconductivity is “turned back on” for Nd3+ (f3), 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.
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