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

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.

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Cited by in corpus (16)

• Symmetry-Breaking Polymorphous Descriptions for Complex Materials without Interelectronic U
• Mass enhancement in 3d and s-p perovskites from symmetry breaking
• Electron-Lattice Interplays in LaMnO3 from Canonical Jahn-Teller Distortion Notations
• Cooperative cluster-Jahn-Teller effect as a possible route to antiferroelectricity
• Density Functional description of spin, lattice, and spin-lattice dynamics in antiferromagnetic and paramagnetic phases at finite temperatures
• Dependence of band gaps in d-electron perovskite oxides on magnetism
• Oxygen magnetic polarization, nodes in spin density, and zigzag spin order in oxides
• Symmetry breaking in vanadium trihalides
• Persistent half-metallic ferromagnetism in a (111)-oriented manganite superlattice
• Exploring energy landscapes of charge multipoles using constrained density functional theory
• Energy-lowering symmetry breaking creates a flat-band insulator in paramagnetic Nb3Cl8
• Decoupling the effects of geometry and nature of strain in LaMnO${}_3$: Interplay of dynamic correlations and uniaxial strain driving magnetic phase transitions
• Multicomponent magneto-orbital order and magneto-orbitons in monolayer VCl3
• Emergent half-metal with mixed structural order in (111)-oriented (LaMnO${}_3$)${}_{2n}$|(SrMnO${}_3$)${}_n$ superlattices
• A possible spin Jahn-Teller material: ordered pseudobrookite FeTi2O5
• Tailoring non-collinear magnetism and 3d $-$ 4f exchange interactions in RVO${}_3$ epitaxial thin films