First-principles study of crystal structural stability and electronic and magnetic properties in LaMn(7)O(12).

The crystal structure, electronic and magnetic properties of LaMn(7)O(12) ((LaMn(3)(3+))(A)Mn(4)(3+)O(12)) are investigated by GGA (LSDA) and GGA + U (LSDA + U) (0.0 ≤ U ≤ 5.0 eV) methods. Based on two experimentally refined structures (distinguished by the distortion parameter Δ, namely S(I) (Δ = 8.5 × 10(-5)) and S(II) (Δ = 25.0 × 10(-4))), GGA and GGA + U with U < 3.0 eV calculations indicate that S(I) with a small distortion is the lowest-energy crystal structure while GGA + U with 3.0 ≤ U ≤ 5.0 eV calculations show that S(II) with a larger distortion is the ground-state crystal structure. Within the LSDA method, S(II) is always the ground-state structure no matter if U is considered or not. There are two independent magnetic sublattices: Mn(3+) within the A site and Mn(3+) within the B site. First, it is predicted that A-site Mn(3+) ions are preferably AFM-coupled in G-type (antiferromagnetically coupled in three directions). Based on this result, four magnetic configurations (FM-[Formula: see text], AFM1-[Formula: see text], AFM2-[Formula: see text] and AFM3-[Formula: see text]) are designed, and their total energies are calculated. Our results demonstrate that AFM2 and AFM3 are the lowest magnetic state, respectively, for S(I) and S(II). Correspondingly, LaMn(7)O(12) is metallic with no orbital ordering at AFM2 for S(I) while it is an insulator with orbital ordering at AFM3 for S(II). Thus, modulation of the distortion parameter Δ, e.g. by chemical doping, could be employed as a new avenue to induce a magnetic phase transition and the corresponding metal-to-insulator transition in LaMn(7)O(12).