Iron spin crossover and its influence on post-perovskite transitions in MgSiO$_3$ and MgGeO$_3$

Abstract

MgGeO$_3$-perovskite is known to be a low-pressure analog of MgSiO$_3$-perovskite in many respects, but especially in regard to the post-perovskite transition. As such, investigation of spin state changes in Fe-bearing MgGeO$_3$ might help to clarify some aspects of this type of state change in Fe-bearing MgSiO$_3$. Using DFT+U calculations, we have investigated pressure induced spin state changes in Fe$^{2+}$ and Fe$^{3+}$ in MgGeO$_3$ perovskite and post-perovskite. Owing to the relatively larger atomic size of germanium compared to silicon, germanate phases have larger unit cell volume and inter-atomic distances than equivalent silicate phases at same pressures. As a result, all pressure induced state changes in iron occur at higher pressures in germanate phases than in the silicate ones, be it a spin state change or position change of (ferrous) iron in the perovskite cage. We showed that iron state transitions occur at particular average Fe-O bond-length irrespective of mineral composition (silicate or germanate) or functionals (LDA+U$_{sc}$ or GGA+U$_{sc}$). Ferrous iron substitution decreases the perovskite to post-perovskite (PPv) transition pressure while coupled ferric iron substitution increases it noticeably.