Cation-deficient lanthanum manganite oxides: Experimental and theoretical studies

Cation-deficient lanthanum manganite oxides with 0.8 ≤ La/Mn ≤ 1.25 were synthesized using a multi-step decomposition of gel precursors and investigated from experimental and theoretical point of view. The XRD (X-Ray Diffraction) analysis of the mixed LaMnO₃ oxide crystal concludes to a hexagonal structure, space group R-3c, excluding the presence of pure oxides such as La₂O₃, Mn₂O₃, or MnO₂ whatever the ratio La/Mn is. Oxides with nominal formulae La_1?xMnO_3+y and LaMn_1?x′O_3+y contain more than one defect structure involving valence defect (holes h), anionic vacancies as well as cationic vacancies in A and B sublattices of the perovskite structure. With the increase of La or Mn non-stoichiometry, the oxygen content y decreases more with La-deficient compositions than with Mn-deficient ones. The La/Mn ratio influences strongly the relationship between h], V_O], V_La^?] and V_Mn^?].The DFT-GGA (Density functional Theory, Generalized-Gradient Approximation) simulation of these compounds using VASP (Vienna Ab-initio Simulation Package) concludes that the electronic structure for the optimized stoichiometric La₆Mn₆O₁₈ is not optimal, relative to that expected considering Mn(III) ions with four alpha electrons each. The non-stoichiometry is the easiest way of reducing the Jahn–Teller instability by depopulating the half-filled e_g orbitals. A partial oxidation is then stabilizing. Creation of defects, either an O insertion or a cationic vacancy, allows finding an ideal count. In the case of pure cationic defects (missing a La(III) or a Mn(III) cation), the amount of vacancies is one missing cation upon twelve. The compact nature of lanthanum manganite oxide does not allow oxygen insertion within the bulk structure and oxidation can only be achieved at the surface without O penetration. The formation of antisites is endothermic. The creation of mixed vicinal vacancies, one oxygen and one cationic vacancy (La or Mn), is exothermic for a concentration of defects of one defect per twelve cations.