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Title: Successes and failures of Hubbard-corrected density functional theory. The case of Mg doped LiCoO 2

Abstract

We have evaluated the successes and failures of the Hubbard-corrected density functional theory approach to study Mg doping of LiCoO 2. We computed the effect of the U parameter on the energetic, geometric, and electronic properties of two possible doping mechanisms: (1) substitution of Mg onto a Co (or Li) site with an associated impurity state and (2) formation of impurity-state-free complexes of substitutional Mg and point defects in LiCoO 2. We find that formation of impurity states results in changes on the valency of Co in LiCoO 2. Variation of the Co U shifts the energy of the impurity state, resulting in energetic, geometric, and electronic properties that depend significantly on the specific value of U. In contrast, the properties of the impurity-state-free complexes are insensitive to U. These results identify reasons for the strong dependence on the doping properties on the chosen value of U and for the overall difficulty of achieving agreement with the experimentally known energetic and electronic properties of doped transition metal oxides such as LiCoO 2.

Authors:
 [1];  [1];  [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1163579
DOE Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 16; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Santana Palacio, Juan A., Kim, Jeongnim, Kent, Paul R., and Reboredo, Fernando A. Successes and failures of Hubbard-corrected density functional theory. The case of Mg doped LiCoO2. United States: N. p., 2014. Web. doi:10.1063/1.4899040.
Santana Palacio, Juan A., Kim, Jeongnim, Kent, Paul R., & Reboredo, Fernando A. Successes and failures of Hubbard-corrected density functional theory. The case of Mg doped LiCoO2. United States. doi:10.1063/1.4899040.
Santana Palacio, Juan A., Kim, Jeongnim, Kent, Paul R., and Reboredo, Fernando A. Tue . "Successes and failures of Hubbard-corrected density functional theory. The case of Mg doped LiCoO2". United States. doi:10.1063/1.4899040. https://www.osti.gov/servlets/purl/1163579.
@article{osti_1163579,
title = {Successes and failures of Hubbard-corrected density functional theory. The case of Mg doped LiCoO2},
author = {Santana Palacio, Juan A. and Kim, Jeongnim and Kent, Paul R. and Reboredo, Fernando A.},
abstractNote = {We have evaluated the successes and failures of the Hubbard-corrected density functional theory approach to study Mg doping of LiCoO2. We computed the effect of the U parameter on the energetic, geometric, and electronic properties of two possible doping mechanisms: (1) substitution of Mg onto a Co (or Li) site with an associated impurity state and (2) formation of impurity-state-free complexes of substitutional Mg and point defects in LiCoO2. We find that formation of impurity states results in changes on the valency of Co in LiCoO2. Variation of the Co U shifts the energy of the impurity state, resulting in energetic, geometric, and electronic properties that depend significantly on the specific value of U. In contrast, the properties of the impurity-state-free complexes are insensitive to U. These results identify reasons for the strong dependence on the doping properties on the chosen value of U and for the overall difficulty of achieving agreement with the experimentally known energetic and electronic properties of doped transition metal oxides such as LiCoO2.},
doi = {10.1063/1.4899040},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 16,
volume = 141,
place = {United States},
year = {2014},
month = {10}
}

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