Covalency, double-counting and the metal-insulator phase diagram in transition metal oxides

TL;DR

This paper uses dynamical mean field theory to explore how d-electron count influences the metal-insulator transition in transition metal oxides, highlighting the importance of double counting corrections and lattice distortions.

Contribution

It demonstrates that d-electron occupancy, controlled by charge transfer, is crucial for the Mott transition and clarifies the role of double counting corrections in density functional methods.

Findings

Insulating behavior occurs only within a narrow d-occupancy range.

d-occupancy in nickelates is far from the Mott boundary, unlike in cuprates.

Lattice distortions are key to the insulating phase in nickelates.

Abstract

Dynamical mean field theory calculations are used to show that for late transition-metal-oxides a critical variable for the Mott/charge-transfer transition is the number of d-electrons, which is determined by charge transfer from oxygen ions. Insulating behavior is found only for a narrow range of d-occupancy, irrespective of the size of the intra-d Coulomb repulsion. The result is useful in interpreting 'density functional +U' and 'density functional plus dynamical mean field' methods in which additional correlations are applied to a specific set of orbitals and an important role is played by the 'double counting correction' which dictates the occupancy of these correlated orbitals. General considerations are presented and are illustrated by calculations for two representative transition metal oxide systems: layered perovskite Cu-based "high-Tc" materials, an orbitally non-degenerate electronically quasi-two dimensional systems, and pseudocubic rare earch nickelates, an orbitally degenerate electronically three dimensional system. Density functional calculations yield d-occupancies very far from the Mott metal-insulator phase boundary in the nickelate materials, but closer to it in the cuprates, indicating the sensitivity of theoretical models of the cuprates to the choice of double counting correction and corroborating the critical role of lattice distortions in attaining the experimentally observed insulating phase in the nickelates.