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

The introduction of magnetic ions at A-site is a typical modification in traditional ABO(3) 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 4d(6) electronic configuration and it splits into t(2g) and eg orbitals (t(2g)(6)e(g)(0)) 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+Mn33+Rh43+O122-. Our study provides an alternative method for beneficial modification of traditional ABO(3) perovskites by introducing A-site magnetic ions.

Automated summary

In this study, 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, revealing that introducing Mn3+ ions at the A '-site can drive ordered antiparallel spins coupling and lead to antiferromagnetic behavior. Additionally, the B site Rh has a small contribution to the magnetic properties, and LaMn3Rh4O12 exhibits semiconducting behavior.