Origin of the Verwey transition in magnetite: Group theory, electronic structure, and lattice dynamics study

TL;DR

This study combines group theory, electronic structure calculations, and lattice dynamics to elucidate the origin of the Verwey transition in magnetite, emphasizing the role of local electron interactions and electron-phonon coupling in driving the metal-insulator transition.

Contribution

It demonstrates that local electron interactions and their coupling to lattice vibrations are crucial for understanding the Verwey transition, providing a comprehensive scenario for its origin.

Findings

Order parameters with specific symmetries induce structural change.

Local electron interactions are essential for accurate phonon dispersion.

Electron interactions amplify electron-phonon coupling, leading to the gap opening.

Abstract

The Verwey phase transition in magnetite has been analyzed using the group theory methods. It is found that two order parameters with the symmetries $X_3$ and $\Delta_5$ induce the structural transformation from the high-temperature cubic to the low-temperature monoclinic phase. The coupling between the order parameters is described by the Landau free energy functional. The electronic and crystal structure for the cubic and monoclinic phases were optimized using the {\it ab initio} density functional method. The electronic structure calculations were performed within the generalized gradient approximation including the on-site interactions between 3d electrons at iron ions -- the Coulomb element $U$ and Hund's exchange $J$. Only when these local interactions are taken into account, the phonon dispersion curves, obtained by the direct method for the cubic phase, reproduce the experimental data. It is shown that the interplay of local electron interations and the coupling to the lattice drives the phonon order parameters and is responsible for the opening of the gap at the Fermi energy. Thus, it is found that the metal-insulator transition in magnetite is promoted by local electron interactions, which significantly amplify the electron-phonon interaction and stabilize weak charge order coexisting with orbital order of the occupied $t_{2g}$ states at Fe ions. This provides a scenario to understand the fundamental problem of the origin of the Verwey transition in magnetite.