High-pressure decomposition of MCr2O4 spinels (M=Mg, Mn, Zn) by ab initio methods

The high-pressure equation of state of the normal spinels MgCr2O4 (picrochr omite), MnCr2O4 and ZnCr2O4, and their reaction of decomposition into Cr2O3 (eskolaite) and MO (rocksalt-type) component oxides, were investigated by periodic unrestricted Hartree-Fock calculations. All-electron basis sets, a nd an a posteriori correction for the electron correlation energy, based on Density-Functional-Theory, were employed. Interpolation of results by the P-V Murnaghan equation of state yielded the equilibrium volume and energy, and the bulk modulus and its pressure derivative, for each of the seven pha ses (three spinels, three rocksalt oxides and eskolaite) considered. The si mulated behaviour of interatomic distances vs pressure shows similar compre ssibilities of MO bonds in both octahedral and tetrahedral coordinations. B inding energies and formation enthalpies of spinels from oxides are also co mputed and compared to available experimental data. The predicted decomposi tion pressures of Mg, Mn and Zn chromium spinels are 19, 23 and 34 GPa, res pectively. The greater stability of ZnCr2O4 is related to Zn2+ being better suited to tetrahedral coordination than the other M2+ cations. Such result s are strongly supported by the excellent agreement previously obtained bet ween simulated (11 GPa) and experimental (13 GPa) pressures of the decompos ition of MgAl2O4 spinel into corundum and periclase.