Displacive Jahn–Teller Transition in NaNiO 2

Nagle-Cocco, Liam A V; Genreith-Schriever, Annalena R.; Steele, James M A; Tacconis, Camilla; Bocarsly, Joshua D.; Mathon, Olivier; Neuefeind, Joerg C; Liu, Jue; O’Keefe, Christopher A.; Goodwin, Andrew L; Grey, Clare P; Evans, John S. O.; Dutton, Siân E; Nagle-Cocco, Liam A. V.; Steele, James M. A.; Neuefeind, Joerg C.; Goodwin, Andrew L.; Grey, Clare P.; Dutton, Siân E.

Abstract

Below its Jahn–Teller transition temperature, T JT, NaNiO2 has a monoclinic layered structure consisting of alternating layers of edge-sharing NaO6 and Jahn–Teller-distorted NiO6 octahedra. Above T JT 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 JT. 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.

Citation

Nagle-Cocco, L. A. V., Genreith-Schriever, A. R., Steele, J. M. A., Tacconis, C., Bocarsly, J. D., Mathon, O., Neuefeind, J. C., Liu, J., O’Keefe, C. A., Goodwin, A. L., Grey, C. P., Evans, J. S. O., Dutton, S. E., Nagle-Cocco, L. A. V., Steele, J. M. A., Neuefeind, J. C., Goodwin, A. L., Grey, C. P., & Dutton, S. E. (2024). Displacive Jahn–Teller Transition in NaNiO 2. Journal of the American Chemical Society, 146(43), 29560-29574. https://doi.org/10.1021/jacs.4c09922

• Journal Article Type: Article
• Acceptance Date: Sep 27, 2024
• Online Publication Date: Oct 14, 2024
• Publication Date: Oct 30, 2024
• Deposit Date: Nov 7, 2024
• Publicly Available Date: Nov 7, 2024
• Journal: Journal of the American Chemical Society
• Print ISSN: 0002-7863
• Electronic ISSN: 1520-5126
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 146
• Issue: 43
• Pages: 29560-29574
• DOI: https://doi.org/10.1021/jacs.4c09922
• Public URL: https://durham-repository.worktribe.com/output/3043668