Modeling of a Cubic Antiferromagnetic Cuprate Super-Cage

Abstract

Convex polyhedral cuprate clusters are being formed through lateral frustration when the a and c lattice parameters of the tetragonal ACuO2 infinite layer structure will become identical by substitution of a large cation (A = Ba2+). However, the corner-shared CuO2 plaquettes of the infinite network suffer a topotactic rearrangement forming edge-connected units, for instance Cu18O24 cages (polyhedron notation [4641238]) with <90˚ ferromagnetic super-exchange interaction as found in cubic BaCuO2. Cage formation via a hypothetical tetragonal BaCuO2 compound (space group P4/ nmm) will be discussed. The possibility to construct a cuprate super-cage with m3m symmetry (polyhedron notation [4641242438]) is being reported. This super-cage still consists of edge-connected CuO2 plaquettes when fully decorated with copper ions, but with different curvatures, arranged in circles of 9.39 Å of diameter with 139.2˚ Cu-O-Cu antiferromagnetic super-exchange interaction. On the one hand, the realization of such a quite stable cuprate super-cage as a candidate for high-Tc superconductivity depends on whether a template of suitable size such as the cation or C(CH3)4 enables its formation, and on the other hand the cage can further be stabilized by highly charged cations located along the [111] direction. Synthesis options will be proposed based on suggested cage formation pathways. An X-ray powder pattern was calculated for a less dense cluster structure of Im3m space group with a lattice parameter of a = 14.938 Å and two formula units of Cu46O51 to facilitate future identification. Characteristic X-ray scattering features as identification tool were obtained when the electron distribution of the hollow polyhedron was approximated with electron density in a spherical shell.