Review of Systematic Tendencies in (001), (011) and (111) Surfaces Using B3PW as Well as B3LYP Computations of BaTiO3, CaTiO3, PbTiO3, SrTiO3, BaZrO3, CaZrO3, PbZrO3 and SrZrO3 Perovskites

Roberts I Eglitis; Ran Jia

doi:10.3390/ma16247623

Review of Systematic Tendencies in (001), (011) and (111) Surfaces Using B3PW as Well as B3LYP Computations of BaTiO₃, CaTiO₃, PbTiO₃, SrTiO₃, BaZrO₃, CaZrO₃, PbZrO₃ and SrZrO₃ Perovskites

Materials (Basel). 2023 Dec 13;16(24):7623. doi: 10.3390/ma16247623.

Authors

Roberts I Eglitis¹, Ran Jia^{1

2}

Affiliations

¹ Institute of Solid State Physics, University of Latvia, 8 Kengaraga Str., LV1063 Riga, Latvia.
² Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China.

Abstract

We performed B3PW and B3LYP computations for BaTiO₃ (BTO), CaTiO₃ (CTO), PbTiO₃ (PTO), SrTiO₃ (STO), BaZrO₃ (BZO), CaZrO₃ (CZO), PbZrO₃ (PZO) and SrZrO₃ (SZO) perovskite neutral (001) along with polar (011) as well as (111) surfaces. For the neutral AO- as well as BO₂-terminated (001) surfaces, in most cases, all upper-layer atoms relax inwards, although the second-layer atoms shift outwards. On the (001) BO₂-terminated surface, the second-layer metal atoms, as a rule, exhibit larger atomic relaxations than the second-layer O atoms. For most ABO₃ perovskites, the (001) surface rumpling s is bigger for the AO- than BO₂-terminated surfaces. In contrast, the surface energies, for both (001) terminations, are practically identical. Conversely, different (011) surface terminations exhibit quite different surface energies for the O-terminated, A-terminated and BO-terminated surfaces. Our computed ABO₃ perovskite (111) surface energies are always significantly larger than the neutral (001) as well as polar (011) surface energies. Our computed ABO₃ perovskite bulk B-O chemical bond covalency increases near their neutral (001) and especially polar (011) surfaces.

Keywords: B3LYP functional; B3PW and B3LYP computations; B3PW functional; BaTiO3 (011) surface; PbTiO3 (111) surface; PbZrO3 (011) surface; SrTiO3 (001) surface; SrZrO3 (001) surface; polar surfaces; surface energies.

Publication types

Review

Grants and funding

This study was funded by the Latvian Council of Science Grant Number: LZP-2021/1-464. The Institute of Solid State Physics, University of Latvia (Latvia), as the Centre of Excellence, has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD01-2016-2017-Teaming Phase2 under Grant Agreement No. 739508, project CAMART-2.