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Title: Rationalization of the Hubbard U parameter in CeO{sub x} from first principles: Unveiling the role of local structure in screening

Abstract

The density functional theory (DFT)+U method has been widely employed in theoretical studies on various ceria systems to correct the delocalization bias in local and semi-local DFT functionals with moderate computational cost. We present a systematic and quantitative study, aiming to gain better understanding of the dependence of Hubbard U on the local atomic arrangement. To rationalize the Hubbard U of Ce 4f, we employed the first principles linear response method to compute Hubbard U for Ce in ceria clusters, bulks, and surfaces. We found that the Hubbard U varies in a wide range from 4.3 eV to 6.7 eV, and exhibits a strong correlation with the Ce coordination number and Ce–O bond lengths, rather than the Ce 4f valence state. The variation of the Hubbard U can be explained by the changes in the strength of local screening due to O → Ce intersite transitions.

Authors:
;  [1]
  1. Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973 (United States)
Publication Date:
OSTI Identifier:
22255076
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 140; Journal Issue: 8; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BOND LENGTHS; DENSITY FUNCTIONAL METHOD; EV RANGE; SURFACES

Citation Formats

Lu, Deyu, and Liu, Ping. Rationalization of the Hubbard U parameter in CeO{sub x} from first principles: Unveiling the role of local structure in screening. United States: N. p., 2014. Web. doi:10.1063/1.4865831.
Lu, Deyu, & Liu, Ping. Rationalization of the Hubbard U parameter in CeO{sub x} from first principles: Unveiling the role of local structure in screening. United States. doi:10.1063/1.4865831.
Lu, Deyu, and Liu, Ping. Fri . "Rationalization of the Hubbard U parameter in CeO{sub x} from first principles: Unveiling the role of local structure in screening". United States. doi:10.1063/1.4865831.
@article{osti_22255076,
title = {Rationalization of the Hubbard U parameter in CeO{sub x} from first principles: Unveiling the role of local structure in screening},
author = {Lu, Deyu and Liu, Ping},
abstractNote = {The density functional theory (DFT)+U method has been widely employed in theoretical studies on various ceria systems to correct the delocalization bias in local and semi-local DFT functionals with moderate computational cost. We present a systematic and quantitative study, aiming to gain better understanding of the dependence of Hubbard U on the local atomic arrangement. To rationalize the Hubbard U of Ce 4f, we employed the first principles linear response method to compute Hubbard U for Ce in ceria clusters, bulks, and surfaces. We found that the Hubbard U varies in a wide range from 4.3 eV to 6.7 eV, and exhibits a strong correlation with the Ce coordination number and Ce–O bond lengths, rather than the Ce 4f valence state. The variation of the Hubbard U can be explained by the changes in the strength of local screening due to O → Ce intersite transitions.},
doi = {10.1063/1.4865831},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 8,
volume = 140,
place = {United States},
year = {2014},
month = {2}
}