Displacive Jahn–Teller Transition in NaNiO<sub>2</sub>
Below its Jahn-Teller transition temperature, <i>T</i><sub>JT</sub>, NaNiO<sub>2</sub> has a monoclinic layered structure consisting of alternating layers of edge-sharing NaO<sub>6</sub> and Jahn-Teller-distorted NiO<sub>6</sub> octahedra. Above <i>T</i><sub>JT</sub> where NaNiO<sub>2</sub> 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 <i>T</i><sub>JT</sub>. This is supported by <i>ab initio</i> 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.
Authors
- Joshua D. Bocarsly (ORCID: https://orcid.org/0000-0002-7523-152X)
- Siân E. Dutton (ORCID: https://orcid.org/0000-0003-0984-5504)
- Olivier Mathon (ORCID: https://orcid.org/0000-0002-5487-0226)
- Jöerg C. Neuefeind (ORCID: https://orcid.org/0000-0002-0563-1544)
- James Mark Alexander Steele (ORCID: https://orcid.org/0000-0002-1075-3634)
- Annalena R. Genreith‐Schriever (ORCID: https://orcid.org/0000-0001-5626-2438)
- John S. O. Evans (ORCID: https://orcid.org/0000-0001-6305-6341)
- Christopher A. O’Keefe (ORCID: https://orcid.org/0000-0003-3115-0768)
- Liam A. V. Nagle‐Cocco (ORCID: https://orcid.org/0000-0001-9265-1588)
- Clare P. Grey (ORCID: https://orcid.org/0000-0001-5572-192X)
- Andrew L. Goodwin (ORCID: https://orcid.org/0000-0001-9231-3749)
- Jue Liu (ORCID: https://orcid.org/0000-0002-4453-910X)
- Camilla Tacconis (ORCID: https://orcid.org/0000-0003-1128-1023)
Institutions
- Oak Ridge National Laboratory (US)
- Durham University (GB)
- University of Cambridge (GB)
- European Synchrotron Radiation Facility (FR)
- University of Oxford (GB)
- China Spallation Neutron Source (CN)
- Universitas Islam Syekh Yusuf (ID)
- Spallation Neutron Source
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2024-10-14
- DOI
- https://doi.org/10.1021/jacs.4c09922
- Citations
- 15
- Primary Topic
- Magnetic and transport properties of perovskites and related materials
- Type
- article
- Field-Weighted Citation Impact
- 1.77
Funders
- Cambridge Philosophical Society
- Faraday Institution
- Engineering and Physical Sciences Research Council
- European Research Council