Evidence for a different electronic configuration as a primary effect during compression of orthorhombic perovskites: The case of NdM3+ O3 (M=Cr, Ga)

Abstract

(Mg,Fe)SiO3 perovskite is the most abundant mineral of the Earth's lower mantle, and compounds with the perovskite structure are perhaps the most widely employed ceramics. Hence, they attract both geophysicists and material scientists. Several investigations attempted to predict their structural evolution at high pressure, and recent advancements highlighted that perovskites having ions with the same formal valence at both polyhedral sites (i.e., 3+:3+) define different compressional patterns when transition metal ions (TMI) are involved. In this study, in situ high-pressure synchrotron XRD measurements coupled with ab initio simulations of the electronic population of NdCrO3 perovskite are compared with the compressional feature of NdGaO3. Almost identical from a steric point of view (Cr3+ and Ga3+ have almost the same ionic radius), the different electronic configuration of octahedrally coordinated ions - which leads to a redistribution of electrons at the 3d orbitals for Cr3+ - allows the crystal field stabilization energy (CFSE) to act as a vehicle of octahedral softening in NdCrO3 or it turns octahedra into rigid units when CFSE is null as in NdGaO3. Besides to highlight that different electronic configurations can act as a primary effect during compression of perovskite compounds, our findings have a deep repercussion on the way the compressibility of perovskites have to be modeled.