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Title: Jahn-Teller mediated ordering in layered Li{sub x}MO{sub 2} compounds

Abstract

Lithium ordering in layered Li{sub x}MO{sub 2} compounds (M=Ni,Co,Mn) is investigated with first-principles calculations. We found that apart from the in-plane Li-Li interactions, the stability of ordered Li{sub x}MO{sub 2} structures strongly depends on the interlayer Li-Li interactions through the M cations. When several stacking sequences are possible, the selection of stacking is shown to be driven by the electronic structure of the transition-metal cations (metallic for Co{sup +3/+4}, localized for Ni{sup +3/+4} and Mn{sup +3/+4}). In Li{sub x}CoO{sub 2} the stacking is chosen so as to minimize the variations in coordination of the symmetrically different Co sites, thus enhancing electronic charge delocalization. In Li{sub x}NiO{sub 2}, lithium ordering couples to orbital and Jahn-Teller ordering so as to form 180{sup o} Li-O-Ni{sup +3}-O-Li complexes. The presence of these 180{sup o} Li{sub A}-O-M-O-Li{sub B} interactions ensures distinct M environments and charge localization. We indicate how the coupling between the e{sub g}{sup *} and Li-2s orbital hybridization and the Jahn-Teller distortion produces a long-range attractive interaction between Li ions.

Authors:
; ;
Publication Date:
Sponsoring Org.:
(US)
OSTI Identifier:
40205468
Resource Type:
Journal Article
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 63; Journal Issue: 14; Other Information: DOI: 10.1103/PhysRevB.63.144107; Othernumber: PRBMDO000063000014144107000001; 042114PRB; PBD: 1 Apr 2001; Journal ID: ISSN 0163-1829
Publisher:
The American Physical Society
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; CATIONS; ELECTRONIC STRUCTURE; HYBRIDIZATION; LITHIUM; STABILITY

Citation Formats

Arroyo y de Dompablo, M. E., Marianetti, C, Van der Ven, A, and Ceder, G. Jahn-Teller mediated ordering in layered Li{sub x}MO{sub 2} compounds. United States: N. p., 2001. Web. doi:10.1103/PhysRevB.63.144107.
Arroyo y de Dompablo, M. E., Marianetti, C, Van der Ven, A, & Ceder, G. Jahn-Teller mediated ordering in layered Li{sub x}MO{sub 2} compounds. United States. doi:10.1103/PhysRevB.63.144107.
Arroyo y de Dompablo, M. E., Marianetti, C, Van der Ven, A, and Ceder, G. Sun . "Jahn-Teller mediated ordering in layered Li{sub x}MO{sub 2} compounds". United States. doi:10.1103/PhysRevB.63.144107.
@article{osti_40205468,
title = {Jahn-Teller mediated ordering in layered Li{sub x}MO{sub 2} compounds},
author = {Arroyo y de Dompablo, M. E. and Marianetti, C and Van der Ven, A and Ceder, G},
abstractNote = {Lithium ordering in layered Li{sub x}MO{sub 2} compounds (M=Ni,Co,Mn) is investigated with first-principles calculations. We found that apart from the in-plane Li-Li interactions, the stability of ordered Li{sub x}MO{sub 2} structures strongly depends on the interlayer Li-Li interactions through the M cations. When several stacking sequences are possible, the selection of stacking is shown to be driven by the electronic structure of the transition-metal cations (metallic for Co{sup +3/+4}, localized for Ni{sup +3/+4} and Mn{sup +3/+4}). In Li{sub x}CoO{sub 2} the stacking is chosen so as to minimize the variations in coordination of the symmetrically different Co sites, thus enhancing electronic charge delocalization. In Li{sub x}NiO{sub 2}, lithium ordering couples to orbital and Jahn-Teller ordering so as to form 180{sup o} Li-O-Ni{sup +3}-O-Li complexes. The presence of these 180{sup o} Li{sub A}-O-M-O-Li{sub B} interactions ensures distinct M environments and charge localization. We indicate how the coupling between the e{sub g}{sup *} and Li-2s orbital hybridization and the Jahn-Teller distortion produces a long-range attractive interaction between Li ions.},
doi = {10.1103/PhysRevB.63.144107},
journal = {Physical Review B},
issn = {0163-1829},
number = 14,
volume = 63,
place = {United States},
year = {2001},
month = {4}
}