Stabilization of A-site ordered perovskites and formation of spin-half antiferromagnetic lattice: CaCu$_3$Ti$_4$O$_{12}$ and CaCu$_3$Zr$_4$O$_{12}$

Abstract: A-site ordered perovskites, CaCu$3$B$_4$O${12}$, which are derivatives of conventional ABO$3$ perovskites, exhibit varying electronic and magnetic properties. With the objective of examining the role of Cu in this work, we have studied CaCu$_3$Ti$_4$O${12}$ and CaCu$3$Zr$_4$O${12}$ and presented the cause of the crystallization of A-site ordered perovskite from conventional ABO$3$ perovskite and the underlying mechanism leading to the stabilization of non-trivial and experimentally estabilished G-type antiferromagnetic (G-AFM) ordering in these systems. The first-principles electronic structure calculations supplemented with phonon studies show that the formation of A-site ordered perovskite is driven by Jahn-Teller distortion of the CuO${12}$ icosahedron. The crystal orbital Hamiltonian population analysis and magnetic exchange interactions estimated using spin dimer analysis infers that the nearest and next-nearest-neighbor interactions (J$_1$ and J$_2$) are direct and weakly ferromagnetic whereas the third-neighbor interaction (J$_3$) is unusually strong and antiferromagnetic driven by indirect superexchange mechanism. The structural geometry reveals that stabilization of G-AFM requires J$_1$ $<$ 2J$_2$, J$_1$ $<$ 2J$_3$. The experimental and theoretical values of Neel Temperature agrees well for $U$ $\approx$ 7 eV, highlighting the role of strong correlation. The magnetic ordering is found to be robust against pressure and strain.