Using variable temperature total and resonant x-ray scattering at the K edge of Ir species, we study the “bad metal” to insulator transition in BaIrO₃, a canonical third transition series oxide. The usage of advanced experimental techniques and large-scale computer modeling helps us show that, contrary to the widely accepted view, charge disproportionation leading to the formation of Ir-trimers with a different number of 5d valence electrons already exists at room temperature. The charge disbalance between the trimers does not evolve much with decreasing temperature while local lattice distortions do, suggesting that the latter and not the former make a key contribution to the emergence of the enigmatic ferromagnetic insulator state of BaIrO₃. The conclusion is supported by DFT calculations based on unmodified experimental structure data. Our work calls for a reconsideration of the role of lattice distortions in determining the electronic properties of third transition series oxides. It also charts a path to assessing these properties on a realistic and not assumed crystal structure basis.
Petkov et al. (Wed,) studied this question.