Crystal morphology and surface structures of orthorhombic MgSiO3 in the presence of divalent impurity ions

Many rheological and transport properties of rocks are determined by the grain boundary structures of their constituent minerals. These grain boundaries often also hold a high concentration of dopant ions. Here, as a first step towards modelling the transport and rheological behaviour of the lower mantle, we report the results of lattice static simulations on the surface structures of Fe²⁺ and Ca²⁺-doped orthorhombic MgSiO₃-perovskite. For all the surfaces we studied, the energies of the doped structures are lowered, sometimes by more than 1 J/m², with respect to the pure surfaces. From our calculated crystal morphologies, we predict that the grains become more tabular as the concentration of Fe²⁺ ions increases, while under equilibrium conditions the grains are cubic. By calculating the replacement energies of Mg²⁺ by Fe²⁺ and Ca²⁺ ions in the six outermost surface layers, we conclude that these divalent ions would tend to segregate onto the crystal surfaces. We suggest, therefore, that the grain boundary structure and rheology of MgSiO₃-perovskite dominated rocks will be strongly affected by the presence of minor elements in the lower mantle.