Origins Vs. fingerprints of the Jahn-Teller effect in d-electron ABX$_3$ perovskites

TL;DR

This paper investigates the origins and fingerprints of the Jahn-Teller effect in ABX3 perovskites, analyzing electronic and structural factors that drive or suppress distortions across different compounds.

Contribution

It provides a comprehensive analysis of the driving forces behind Jahn-Teller distortions, clarifying when they are electronically driven or suppressed in various perovskites.

Findings

Identifies compounds with electronically-driven Jahn-Teller distortions like KCrF3 and LaVO3.

Explains why some compounds with orbital degeneracies do not show Jahn-Teller distortions.

Provides a unified explanation for octahedral deformations without relying on Mott-Hubbard mechanisms.

Abstract

The Jahn-Teller (JT) distortion that can remove electronic degeneracies in partially occupied states and results in systematic atomic displacements is a common underlying feature to many of the intriguing phenomena observed in 3d perovskites, encompassing magnetism, superconductivity, orbital ordering and colossal magnetoresistance. Although the seminal Jahn and Teller theorem has been postulated almost a century ago, the origins of this effect in perovskite materials are still debated, including propositions such as super exchange, spin-phonon coupling, sterically induced lattice distortions, and strong dynamical correlation effects. Here we analyze the driving forces behind the Jahn-Teller motions and associated electronic fingerprints in a full range of ABX3 compounds. We identify (i) compounds that are prone to an electronically-driven instabilities (i.e. a pure JT effect) such as KCrF3, KCuF3 or LaVO3 and proceed to relax the structures, finding quantitatively the JTD in excellent agreement with experiment; (ii) compounds such as LaMnO3 or LaTiO3 that do not show electronically driven JTD despite orbital degeneracies, because their strongly hybridized B, d-X, p states supply but too weak JT forces to overcome the needed atomic distortions; (iii) although LaVO3 exhibits similar B, d-X, p hybridizations as LaTiO3, the former compound exhibits a robust electronic instability while LaTiO3 has zero stabilization energy, the reason being that LaVO3 has two electrons t2g2 relative to LaTiO3 with just one t2g1. (iv) We explain the trends in "orbital ordering" whereby electrons occupy orbitals that point to orthogonal directions between all nearest-neighbor 3d atoms. We thereby provide a unified vision to explain octahedra deformations in perovskites that, at odds with common wisdom, does not require the celebrated Mott-Hubbard mechanism.