Vibrational and Thermodynamic Properties of Hydrous Iron-Bearing Lowermost Mantle Minerals

The vibrational and thermodynamic properties of minerals are key to understanding the phase stability and the thermal structure of the Earth’s mantle. In this study, we modeled hydrous iron-bearing bridgmanite (Brg) and post-perovskite (PPv) with different [Fe3+-H] defect configurations using first-principles calculations combined with quasi-harmonic approximations (QHA). Fe3+-H configurations can be vibrationally stable in Brg and PPv; the site occupancy of this defect will strongly affect its thermodynamic properties and particularly its response to pressure. The presence of Fe3+-H introduces distinctive high-frequency vibrations to the crystal. The frequency of these peaks is configuration dependence. Of the two defect configurations, [FeSi′+OH·] makes large effects on the thermodynamic properties of Brg and PPv, whereas [VMg″+FeMg·+OH·] has negligible effects. With an expected lower mantle water concentrations of <1000 wt. ppm the effect of Fe3+-H clusters on properties such as heat capacity and thermal expansion is negligible, but the effect on the Grüneisen parameter γ can be significant (~1.2%). This may imply that even a small amount of water may affect the anharmonicity of Fe3+-bearing MgSiO3 in lower mantle conditions and that when calculating the adiabaticity of the mantle, water concentrations need to be considered.