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.
Highlights
ABX3 (X = O, F) perovskites [1,2] show a number of systematic atomic distortions relative to the ideal cubic perovskite structure made of corner-sharing, vertically positioned, all-parallel BX6 octahedra with equal B-X bonds
We see that given the opportunity for orbital broken symmetry, the compounds LaVO3, KFeF3, KCoF3, KCrF3, and KCuF3 show an energy gain EOBS−no OBS < 0, with a concomitant opening of the band gap, while LaTiO3 and LaMnO3 have EOBS−no OBS = 0; i.e., the initially imposed OBS relaxes back to the configuration with occupied degenerate orbitals, and the system stays metallic
The results show that for all compounds displaying a spontaneous electronic instability, the lowest-energy state is always associated with configuration (c), e.g., alternation of dx2 and dy2 in all Cartesian directions, forming a 3D checkerboard
Summary
We conclude that the electronically induced Jahn-Teller distortion mode Q2− and the geometrically induced steric Q2+ octahedral deformation mode are fully captured by a static mean-field method This is in line with recent theoretical works that have demonstrated that static mean-field methods capable of inducing broken symmetry such as density functional theory [7,10,21,34] in a polymorphous representation suffice to explain (i) the trends in gapping and type of magnetic order across the ternary ABO3 series [10] and the binary 3d oxide series [8,36]; (ii) the trends in disproportionation into two different local environments of the B site 2ABO3 → A2[B, B ]O6 [9]; and (iii) the explanation of doping Mott insulators including cuprates [37,38], doping kagome structures [39], as well as “antidoping” oxides [40]
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