Electronic correlations in Lix̳ CoO₂

The purpose of this thesis is further the understanding of the electronic properties of LixCoO2 using density functional theory (DFT) and the dynamical mean-field theory (DMFT). Three main problems are addressed. First, the influence of hybridization among the eg and oxygen orbitals is studied using DFT and a modified Hubbard model which is solved within DMFT. It has long been known that doping holes into the t2g bands are accompanied by a rehybridization which causes electron density to be added to the eg states and hole density to the oxygen states. This so-called rehybridization mechanism has been demonstrated to be a competition between the hybridization, which prefers to occupy the eg orbitals, and the Co on-site coulomb repulsion, which prefers to have the eg orbitals empty to avoid the strong coulomb interaction. It is also shown that eg-oxygen hybridization effectively screens the low energy t2g excitations, which has implications for the low energy Hamiltonian corresponding to hydrated Nal/3CoO2. Second, the hereto anomalous first-order metal-insulator transition in LixCoO2 (0.75 < x < 0.95) is identified as a Mott transition of impurity states. DFT supercell calculations indicate that for dilute Li vacancy concentrations (ie x > 0.95), the vacancy potential binds its hole and forms an impurity state which leads to a Mott insulator. We argue that the first-order transition is due to a decomposition of the impurity band, and is perhaps the only known example of a first-order Mott transition in a doped semiconductor. Third, LiCoO2 possesses a high energy photoemission satellite which hereto could not be predicted by any first-principles method. LDA+DMFT solved within multi-band iterated perturbation theory successfully predicts the satellite.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Materials Science and Engineering.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2004

Author dc:creator

• Marianetti, Chris, 1975-

Advisor dc:contributor.advisor

• Gerbrand Ceder.

• Materials Science and Engineering.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/30120

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/30120