Stability of the Ni sites across the pressure-induced metallization in YNiO3

TL;DR

This study investigates the pressure-induced insulator-to-metal transition in YNiO3, revealing that metallization is driven by inter-octahedral rearrangements rather than local NiO6 geometry changes, supported by XAS and ab initio calculations.

Contribution

It demonstrates that the insulator-metal transition in YNiO3 is primarily due to medium-range order changes, not local NiO6 distortions, advancing understanding of bandwidth-driven transitions.

Findings

NiO6 units contract under pressure up to 13 GPa

Metallization correlates with medium-range order changes

Transition driven by inter-octahedral rearrangement

Abstract

The local environment of nickel atoms in Y NiO3 across the pressure- induced insulator to metal (IM) transition was studied using X-ray absorption spectroscopy (XAS) supported by ab initio calculations. The monotonic contraction of the NiO6 units under applied pressure observed up to 13 GPa, stops in a limited pressure domain around 14 GPa, before resuming above 16 GPa. In this narrow pressure range, crystallographic modifications basically occur in the medium/long range, not in the NiO6 octahedron, whereas the evolution of the near-edge XAS features can be associated to metallization. Ab initio calculations show that these features are related to medium range order, provided that the Ni-O-Ni angle enables a proper overlap of the Ni eg and O 2p orbitals. Metallization is then not directly related to modifications in the average local geometry of the NiO6 units but more likely to an inter-octahedra rearrangement. These outcomes provides evidences of the bandwidth driven nature of the IM transition.