Displacive Jahn–Teller transition in NaNiO2

Below its Jahn–Teller transition temperature, T<sub>JT</sub>, NaNiO2 has a monoclinic layered structure consisting of alternating layers of edge-sharing NaO6 and Jahn–Teller-distorted NiO6 octahedra. Above T<sub>JT</sub> where NaNiO2 is rhombohedral, diffraction measurements...

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Bibliographic Details
Main Authors: Nagle-Cocco, LAV, Genreith-Schriever, AR, Steele, JMA, Tacconis, C, Bocarsly, JD, Mathon, O, Neuefeind, JC, Liu, J, O’Keefe, CA, Goodwin, AL, Grey, CP, Evans, JSO, Dutton, S
Format: Journal article
Language:English
Published: American Chemical Society 2024
Description
Summary:Below its Jahn–Teller transition temperature, T<sub>JT</sub>, NaNiO2 has a monoclinic layered structure consisting of alternating layers of edge-sharing NaO6 and Jahn–Teller-distorted NiO6 octahedra. Above T<sub>JT</sub> where NaNiO2 is rhombohedral, diffraction measurements show the absence of a cooperative Jahn–Teller distortion, accompanied by an increase in the unit cell volume. Using neutron total scattering, solid-state Nuclear Magnetic Resonance (NMR), and extended X-ray absorption fine structure (EXAFS) experiments as local probes of the structure we find direct evidence for a displacive, as opposed to order-disorder Jahn–Teller transition at T<sub>JT</sub>. This is supported by ab initio molecular dynamics (AIMD) simulations. To our knowledge this study is the first to show a displacive Jahn–Teller transition in any material using direct observations with local probe techniques.