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  • Letter
  • Open Access

Microscopic picture of paraelectric perovskites from structural prototypes

Michele Kotiuga1,*, Samed Halilov2, Boris Kozinsky3,4, Marco Fornari5, Nicola Marzari1, and Giovanni Pizzi1,†

  • 1Theory and Simulation of Materials (THEOS), National Centre for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland
  • 2Designed Material Technologies, LLC, P.O. Box 14548, Richmond, Virginia 23221-9998, USA
  • 3John A. Paulson School of Engineering and Applied Sciences, Harvard University, 29 Oxford Street, Cambridge, Massachusetts 02138, USA
  • 4Robert Bosch LLC, Research and Technology Center, Cambridge, Massachusetts 02139, USA
  • 5Department of Physics and Science of Advanced Materials Program, Central Michigan University, Mt. Pleasant, Michigan 48859, USA

  • *michele.kotiuga@epfl.ch
  • †giovanni.pizzi@epfl.ch
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Phys. Rev. Research 4, L012042 – Published 29 March, 2022

DOI: https://doi.org/10.1103/PhysRevResearch.4.L012042

Abstract

We highlight with first-principles molecular dynamics the persistence of intrinsic 〈111〉 Ti off-centerings for BaTiO3 in its cubic paraelectric phase. Intriguingly, these are inconsistent with the Pm3¯m space group often used to atomistically model this phase using density-functional theory or similar methods. Therefore, we deploy a systematic symmetry analysis to construct representative structural models in the form of supercells that satisfy a desired point symmetry but are built from the combination of lower-symmetry primitive cells. We define as structural prototypes the smallest of these that are both energetically and dynamically stable. Remarkably, two 40-atom prototypes can be identified for paraelectric BaTiO3; these are also common to many other ABO3 perovskites. These prototypes can offer structural models of paraelectric phases that can be used for the computational engineering of functional materials. Last, we show that the emergence of B-cation off-centerings and the primitive-cell phonon instabilities is controlled by the equilibrium volume, in turn, dictated by the filler A cation.

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Phys. Rev. Research 4, L012042– Published 29 March, 2022
  • Received 9 July 2021
  • Revised 16 February 2022
  • Accepted 18 February 2022
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