First-principles study of structural, electronic and magnetic properties of A-site-ordered quadruple perovskite LaMn3Rh4O12

Abstract The introduction of magnetic ions at A-site is a typical modification in traditional ABO3 perovskite materials to achieve the target physical properties. Here, the impact of Mn3+ incorporation on the magnetic coupling and electronic structures of A-site-ordered quadruple perovskite LaMn3Rh4O12 was investigated using spin-polarized first-principles calculations. Our calculations demonstrate that LaMn3Rh4O12 is antiferromagnetic with G-type antiferromagnetic coupling within Mn sublattice and nonmagnetic Rh, which is quite different from the diamagnetic host perovskite LaRhO3. The electronic structure analyses reveal that the formal oxidation state of B-site Rh is +3 with 4d6 electronic configuration and it splits into t2g and eg orbitals (t2g6eg0) in low-spin state, indicating that Rh has no contribution to the magnetic properties and the introduced Mn3+ at the A′-site drives the ordered antiparallel spins coupling. Moreover, LaMn3Rh4O12 exhibits semiconducting behavior and the chemical valence is La3+Mn3+3Rh3+4O2-12. Our study provides an alternative method for beneficial modification of traditional ABO3 perovskites by introducing A-site magnetic ions.