Ground state oxygen holes and the metal-insulator transition in the negative charge transfer rare-earth nickelates

TL;DR

This study uses advanced spectroscopic techniques to reveal that rare-earth nickelates have oxygen 2p holes in their ground state, supporting a negative charge-transfer model that explains their metal-insulator transition.

Contribution

It provides direct spectroscopic evidence for oxygen 2p holes and confirms the negative charge-transfer nature of rare-earth nickelates, advancing understanding of their electronic structure.

Findings

Presence of oxygen 2p holes in ground state

Spectral signatures from Ni 3d8 configuration and oxygen holes

Supports negative charge-transfer energy model

Abstract

The metal-insulator transitions and the intriguing physical properties of rare-earth perovskite nickelates have attracted considerable attention in recent years. Nonetheless, a complete understanding of these materials remains elusive. Here, taking a NdNiO3 thin film as a representative example, we utilize a combination of x-ray absorption and resonant inelastic x-ray scattering (RIXS) spectroscopies to resolve important aspects of the complex electronic structure of the rare-earth nickelates. The unusual coexistence of bound and continuum excitations observed in the RIXS spectra provides strong evidence for the abundance of oxygen 2p holes in the ground state of these materials. Using cluster calculations and Anderson impurity model interpretation, we show that these distinct spectral signatures arise from a Ni 3d8 configuration along with holes in the oxygen 2p valence band, confirming suggestions that these materials do not obey a conventional positive charge-transfer picture, but instead exhibit a negative charge-transfer energy, in line with recent models interpreting the metal to insulator transition in terms of bond disproportionation.