Reconciling the ionic and covalent pictures in rare-earth nickelates

Abstract

The properties of AMO3 perovskite oxides, where M is a 3d transition metal, depend strongly on the level of covalency between the metal d and oxygen p orbitals. With their complex spin orders and metal-insulator transition, rare-earth nickelates verge between dominantly ionic and covalent characters. Accordingly, the nature of their ground state is highly debated. Here, we reconcile the ionic and covalent visions of the insulating state of nickelates. Through first-principles calculations, we show that it is reminiscent of the ionic charge disproportionation picture (with strictly low-spin 4+ and high-spin 2+ Ni sites) while exhibiting strong covalence effects with oxygen electrons shifted toward the depleted Ni cations, mimicking a configuration with identical Ni sites. Our results further hint at strategies to control electronic and magnetic phases of transition metal oxide perovskites.

References in corpus (7)

• Restoring the density-gradient expansion for exchange in solids and surfaces
• Generalized gradient approximation for solids and their surfaces
• Orbital order and possible superconductivity in LaNiO3/LaMO3 superlattices
• Hybridization-controlled charge transfer and induced magnetism at correlated oxide interfaces
• Low-energy description of the metal-insulator transition in the rare-earth nickelates
• Tunable Charge and Spin Order in PrNiO${}_3$ Thin Films and Superlattices
• Strain Control of Electronic Phase in Rare Earth Nickelates

Cited by in corpus (51)

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• Renormalization of effective interactions in a negative charge-transfer insulator
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• Origin of the orbital and spin orderings in rare-earth titanates
• Confinement- and strain-induced enhancement of thermoelectric properties in LaNiO${}_3$/LaAlO${}_3(001)$ superlattices
• High-density electron doping of SmNiO${}_3$ from first principles
• Distortion mode anomalies in bulk PrNiO${}_3$ illustrating the potential of symmetry-adapted distortion mode analysis for the study of phase transitions
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• Direct Visualization of Spatial inhomogeneity of Spin Stripes Order in La1.72Sr0.28NiO4
• Charge ordering as the driving mechanism for superconductivity in rare-earth nickel oxides
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• Interplay between breathing-mode distortions and magnetic order in rare-earth nickelates from $ab$ $initio$ magnetic models
• DFT-Guided Operando Raman Characterization of Ni-Based Phases Relevant to Electrochemical Systems
• Designing Non-Relativistic Spin Splitting in Oxide Perovskites
• Insulator-bad metal transition in RNiO${}_3$ nickelates beyond Hubbard model and density functional theory
• Heteroanionic Stabilization of Ni${}^{1+}$ with Nonplanar Coordination in Layered Nickelates
• Emergence and tunability of Fermi-pocket and electronic instabilities in layered Nickelates
• Stability and diffusion of oxygen vacancies in LaNiO${}_3$: a DMFT study
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