First principles simulations of the stability and structure of grain boundaries in Mg₂SiO₄ forsterite

Abstract

Our understanding of how grain boundaries (GBs) can dramatically influence key mineral properties such as creep and diffusion depends on knowledge of their detailed atomic and electronic structures. For this purpose, we simulate different types of tilt GBs, (0l1)/[100], (1l0)/[001] and (012)/[100] modeled with stepped and non-stepped surfaces in Mg₂SiO₄ forsterite using a first-principles approach based on density functional theory. Our results suggest that several configurations arising from Mg-terminated planes with tilt angles ranging from 16° to 67° are energetically competitive over the entire pressure regime (0–17 GPa) studied. At the ambient pressure, the predicted important features of the boundaries include distorted bonds (Si–O and Mg–O distances changed by 1 and 4 %, respectively), coordination defects (four and fivefold Mg–O coordination), and void spaces (0.2–0.9 × 10⁻¹⁰ m³/m²). Also, the interface induces splitting of electronic states from the conduction band and kinks at the top of the valence band. These structural and electronic features continue to exist at higher pressures. The formation enthalpy and excess volume for each boundary configuration studied were shown to systematically increase and decrease, respectively, with pressure. The predicted energy range (0.8–1.7 J/m² at zero pressure) widens by a factor of two at 17 GPa (1.1–2.8 J/m²). The presence of low-density and structurally distorted regions imply that these GBs can serve as primary impurity segregation sites, fast diffusion pathways, and electron-trapped regions, which all are relevant for mantle rheology.