Phonon Calculations in Cubic and Tetragonal Phases of SrTiO3: a Comparative LCAO and Plane Wave Study

TL;DR

This study compares LCAO and plane wave methods for phonon calculations in cubic and tetragonal SrTiO3, demonstrating the accuracy of hybrid functionals and analyzing phase transition effects.

Contribution

It provides a comparative analysis of LCAO and plane wave approaches using hybrid functionals for phonon calculations in SrTiO3, highlighting their agreement with experimental data.

Findings

Hybrid PBE0 functional yields best experimental agreement.

LCAO and plane wave methods produce consistent phonon frequencies.

Temperature-dependent free energy and heat capacity match experiments.

Abstract

The atomic, electronic structure and phonon frequencies have been calculated in a cubic and low-temperature tetragonal SrTiO3 phases at the ab initio level. We demonstrate that the use of hybrid exchange-correlation PBE0 functional gives the best agreement with experimental data. The results for the standard PBE and hybrid PBE0 are compared for the two types of basis sets: a linear combination of atomic orbitals (LCAO, CRYSTAL09 computer code) and plane waves (PW, VASP 5.2 code). Relation between cubic and tetragonal antiferrodistortive (AFD) phases and the relevant AFD phase transition observed at 110 K is discussed in terms of group theory and illustrated with analysis of calculated soft mode frequences at the {\Gamma} and R points in the Brillouin zone. Based on phonon calculations, the temperature dependences of the Helmholtz free energy and heat capacity are in a good agreement with experiment.