First-principles and semiempirical Hartree-Fock calculations for F centers in KNbO3 and Li impurities in KTaO3

TL;DR

This study employs first-principles and semi-empirical Hartree-Fock calculations to investigate F centers in KNbO3 and Li impurities in KTaO3, revealing details about defect electronic structure and lattice relaxation.

Contribution

It introduces a combined use of LMTO and INDO methods for defect analysis in ferroelectric perovskites, providing new insights into defect states and impurity relaxations.

Findings

Electrons in F centers are significantly delocalized.

Absorption energies calculated via Delta-SCF scheme.

Li impurities exhibit off-center displacements and unique relaxation patterns.

Abstract

The LMTO method based on the density-functional theory and the semi-empirical INDO method based on the Hartree--Fock formalism are used for the supercell study of the F centers in cubic and orthorhombic ferroelectric KNbO3 crystals. Two electrons are found to be considerably delocalized even in the ground state of the defect. The absorption energies were calculated by means of the INDO method using the Delta-SCF scheme after a relaxation of atoms surrounding the F center. As an example of another type of point defect in perovskite, an isolated Li impurity in KTaO3 as well as interacting Li pairs are considered in the supercell approach, using the supercells of up to 270 atoms. The off-center Li displacement, reorientational energy barriers and the lattice relaxation around impurities are calculated. The results are compared with those obtained earlier within the shell model, revealing the relaxation pattern somehow different from the shell model estimations.