Structural Stability and Properties of Marokite-Type γ-Mn₃O₄

We synthesized single crystals of marokite (CaMn₂O₄)-type orthorhombic manganese (II,III) oxide, γ-Mn₃O₄, in a multianvil apparatus at pressures of 10-24 GPa. The magnetic, electronic, and optical properties of the crystals were investigated at ambient pressure. It was found that γ-Mn₃O₄ is a semiconductor with an indirect band gap E_g of 0.96 eV and two antiferromagnetic transitions (T_N) at ∼200 and ∼55 K. The phase stability of the γ-Mn₃O₄ crystals was examined in the pressure range of 0-60 GPa using single-crystal X-ray diffraction and Raman spectroscopy. A bulk modulus of γ-Mn₃O₄ was determined to be B₀ = 235.3(2) GPa with B' = 2.6(6). The γ-Mn₃O₄ phase persisted over the whole pressure range studied and did not transform or decompose upon laser heating of the sample to ∼3500 K at 60 GPa. This result seems surprising, given the high-pressure structural diversity of iron oxides with similar stoichiometries. With an increase in pressure, the degree of distortion of MnO₆ polyhedra decreased. Furthermore, there are signs indicating a limited charge transfer between the Mn³⁺ ions in the octahedra and the Mn²⁺ ions in the trigonal prisms. Our results demonstrate that the high-pressure behavior of the structural, electronic, and chemical properties of manganese oxides strongly differs from that of iron oxides with similar stoichiometries.