Magnetic Superexchange and Mott Insulator Mechanisms in Cubic Perovskites: From First-Principles to Canonical Models

Abstract

The ground state of many insulating, open-shell transition-metal perovskites with a 180° metal–ligand–metal bridge is antiferromagnetic (AFM), as predicted by Anderson’s superexchange interaction or Hubbard’s model. These well-established, standard models show how these systems are insulators due to the minimization of the interactions between electrons, at the cost of localizing the electrons on the metal ions. In this work, we carry out first-principles simulations on the cubic perovskites KNiF₃ and KVF₃, analyzing electron densities, energies and bond indices. Although our calculations predict an antiferromagnetic ordering (AFM), in agreement with canonical superexchange models, we show through various indicators that the stabilization of this phase is not mainly associated with the antibonding magnetic orbitals but rather with bonding orbitals not included in the models. In particular, these traditional descriptions of superexchange do not adequately describe the ligand-to-metal electronic backdonation, which is an important element for stabilizing the insulating state of the two studied perovskite fluorides, albeit by diametrically different mechanisms: (1) reducing electron–electron repulsion in KNiF₃, as proposed by Hubbard, whereas (2) enhancing electron–nuclear attraction in KVF₃. Our findings highlight some of the limitations of these foundational models and offer a novel perspective on the understanding of magnetism.

The origin of the nonmagnetic (NM) metallic phase instability and the stabilization of the antiferromagnetic (AFM) versus the ferromagnetic (FM) phase have been studied by first-principles calculations on cubic perovskites KMF₃ (M = Ni, V) and compared to canonical superexchange models (Anderson’s, Hubbard’s). We observe changes in the electron density, accounting for the largest part of the energy stabilization, that cannot be described by minimal models that only consider the magnetic orbitals.