Atomic and electronic structure of perfect and defective PbZrO3 perovskite: Hybrid DFT calculations of cubic and orthorhombic phases

S. Piskunov; A. Gopeyenko; E. A. Kotomin; Yu F. Zhukovskii; D. E. Ellis

doi:10.1016/j.commatsci.2007.03.012

Atomic and electronic structure of perfect and defective PbZrO₃ perovskite: Hybrid DFT calculations of cubic and orthorhombic phases

S. Piskunov^*, A. Gopeyenko, E. A. Kotomin, Yu F. Zhukovskii, D. E. Ellis

^*Corresponding author for this work

Physics and Astronomy

Research output: Contribution to journal › Article › peer-review

35 Scopus citations

Abstract

The structural and electronic properties of pure cubic and low-temperature orthorhombic PbZrO₃ (antiferroelectric phase), as well as cubic PbZrO₃ containing single F-centers (neutral oxygen vacancies) have been simulated by means of ab initio hybrid density functional calculations. We observed a substantial increase of the Pb-O bond covalency in ideal orthorhombic PbZrO₃ with respect to its cubic phase. Relatively large displacement of four Pb atoms nearest to the F-center (0.25 Å towards the defect) could affect the PbZrO₃ ferroelectric properties. An O vacancy in the bulk PbZrO₃ attracts ≈0.7 e, and the remaining electron density from the missing O^2- is localized mostly on four nearest Pb atoms. This leads to appearance of an energy level in the middle of the band gap of cubic PbZrO₃, unlike the shallow F-level found in SrTiO₃.

Original language	English (US)
Pages (from-to)	195-201
Number of pages	7
Journal	Computational Materials Science
Volume	41
Issue number	2
DOIs	https://doi.org/10.1016/j.commatsci.2007.03.012
State	Published - Dec 2007

Keywords

Atomic and electronic structure
Cubic and orthorhombic PbZrO phases
Hybrid DFT calculations
Single F-center

ASJC Scopus subject areas

Computer Science(all)
Chemistry(all)
Materials Science(all)
Mechanics of Materials
Physics and Astronomy(all)
Computational Mathematics

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10.1016/j.commatsci.2007.03.012

Cite this

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title = "Atomic and electronic structure of perfect and defective PbZrO3 perovskite: Hybrid DFT calculations of cubic and orthorhombic phases",

abstract = "The structural and electronic properties of pure cubic and low-temperature orthorhombic PbZrO3 (antiferroelectric phase), as well as cubic PbZrO3 containing single F-centers (neutral oxygen vacancies) have been simulated by means of ab initio hybrid density functional calculations. We observed a substantial increase of the Pb-O bond covalency in ideal orthorhombic PbZrO3 with respect to its cubic phase. Relatively large displacement of four Pb atoms nearest to the F-center (0.25 {\AA} towards the defect) could affect the PbZrO3 ferroelectric properties. An O vacancy in the bulk PbZrO3 attracts ≈0.7 e, and the remaining electron density from the missing O2- is localized mostly on four nearest Pb atoms. This leads to appearance of an energy level in the middle of the band gap of cubic PbZrO3, unlike the shallow F-level found in SrTiO3.",

keywords = "Atomic and electronic structure, Cubic and orthorhombic PbZrO phases, Hybrid DFT calculations, Single F-center",

author = "S. Piskunov and A. Gopeyenko and Kotomin, {E. A.} and Zhukovskii, {Yu F.} and Ellis, {D. E.}",

note = "Funding Information: Authors kindly thank R. Caciuffo, E. Heifets, E. Klotins and A. Sternberg for numerous fruitful discussions. This study was supported by the MRSEC program of the National Science Foundation (DMR-0076091) and EUROATOM-Fusion-Latvia. S.P. gratefully acknowledges also funding from the European Social Fund (ESF). Copyright: Copyright 2008 Elsevier B.V., All rights reserved.",

year = "2007",

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doi = "10.1016/j.commatsci.2007.03.012",

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AU - Gopeyenko, A.

AU - Kotomin, E. A.

AU - Zhukovskii, Yu F.

AU - Ellis, D. E.

N1 - Funding Information: Authors kindly thank R. Caciuffo, E. Heifets, E. Klotins and A. Sternberg for numerous fruitful discussions. This study was supported by the MRSEC program of the National Science Foundation (DMR-0076091) and EUROATOM-Fusion-Latvia. S.P. gratefully acknowledges also funding from the European Social Fund (ESF). Copyright: Copyright 2008 Elsevier B.V., All rights reserved.

PY - 2007/12

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N2 - The structural and electronic properties of pure cubic and low-temperature orthorhombic PbZrO3 (antiferroelectric phase), as well as cubic PbZrO3 containing single F-centers (neutral oxygen vacancies) have been simulated by means of ab initio hybrid density functional calculations. We observed a substantial increase of the Pb-O bond covalency in ideal orthorhombic PbZrO3 with respect to its cubic phase. Relatively large displacement of four Pb atoms nearest to the F-center (0.25 Å towards the defect) could affect the PbZrO3 ferroelectric properties. An O vacancy in the bulk PbZrO3 attracts ≈0.7 e, and the remaining electron density from the missing O2- is localized mostly on four nearest Pb atoms. This leads to appearance of an energy level in the middle of the band gap of cubic PbZrO3, unlike the shallow F-level found in SrTiO3.

AB - The structural and electronic properties of pure cubic and low-temperature orthorhombic PbZrO3 (antiferroelectric phase), as well as cubic PbZrO3 containing single F-centers (neutral oxygen vacancies) have been simulated by means of ab initio hybrid density functional calculations. We observed a substantial increase of the Pb-O bond covalency in ideal orthorhombic PbZrO3 with respect to its cubic phase. Relatively large displacement of four Pb atoms nearest to the F-center (0.25 Å towards the defect) could affect the PbZrO3 ferroelectric properties. An O vacancy in the bulk PbZrO3 attracts ≈0.7 e, and the remaining electron density from the missing O2- is localized mostly on four nearest Pb atoms. This leads to appearance of an energy level in the middle of the band gap of cubic PbZrO3, unlike the shallow F-level found in SrTiO3.

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