A first principle study of the structural, electronic, and magnetic phase transitions in perovskite CaCu₃Co₄O₁₂ via Resubstitution at the Cosite

DFT study was carried out on the structural, electronic, elastic and magnetic properties of the quaternary perovskites CaCu₃Co_4-xRe_xO₁₂ (x = 0, 2, and 4) using GGA + U potential. Through structural optimization, it was observed that CaCu₃Co₂Re₂O₁₂ is stable in the Pn-3 space group and structural phase transition occurs from the Im-3 space group as a result of the substitution of Re at the Co site. CaCu₃Co₂Re₂O₁₂ exhibits higher thermodynamic stability compared to the other compounds, as evidenced by its cohesive energy and enthalpy of formation. The stability of the compounds is also confirmed through phonon calculations. By substituting Re at the Co site, these compounds undergo a transformation from metallic to semi-metallic. Additionally, this substitution also changes the host compound from being ferromagnetic (FM) to non-magnetic through the ferrimagnetic (FiM) spin state. The electrical resistivity of all these compounds confirms the calculated electronic behaviors. These compounds exhibit mechanical stability, with anisotropic behavior and ductile nature. Both CaCu₃Co₄O₁₂ and CaCu₃Co₂Re₂O₁₂ have excellent prospects for use in magnetic storage and spintronics due to their FM and FiM properties, respectively.