Local Electronic Structure of PbVO3, a New Member of PbTiO3 Family, studied by XANES/ELNES

TL;DR

This study investigates the local electronic structure of PbVO3, a new multiferroic material in the PbTiO3 family, using theoretical XANES spectra to understand how tetragonality and temperature affect electronic features.

Contribution

The paper provides the first theoretical analysis of V K-edge XANES spectra in PbVO3, linking electronic structure changes to tetragonality and temperature variations.

Findings

Tetragonality increases monotonically with temperature from 12 K to 570 K.

XANES spectra reveal effects of local symmetry and bond distances on electronic features.

Electronic structure analysis complements recent crystallographic data.

Abstract

Recently an interesting multi-ferroic system PbVO3 [Chem. Mater. 2004] was successfully prepared using a high-pressure and high-temperature technique. The crystallographic features were reported. In this note we concentrate on the theoretical XANES spectra by considering the K-edge of Vanadium. The tetragonality [c/a=1.229 at 300 K] of PbVO3 is the largest in the PbTiO3 family of compounds. Thus one is led naturally to examine the effect of the change of tetragonality and the axial oxygen position on the electronic structure [i.e. XANES spectrum]. We study this effect in two ways. At a given temperature we vary the tetragonality and the axial oxygen position and quantify it in terms of XANES difference spectrum. Secondly, we compute the XANES spectra at three different temperatures, 90 K, 300 K, and 530 K and quantify the change in terms of the difference spectrum. We note that in this compound the tetragonality increases almost monotonically with temperature from 12 K to 570 K without transition to the cubic phase under ambient pressure. A key objective of the current investigation is to gain an understanding of various absorption features in the vicinity of K-edge of V, in terms of valence, local site symmetry, local coordination geometry, local bond distances, charge transfer, and local projected density of states. We consider both the polarized and the unpolarized XANES spectra. In short we have performed a local electronic study, which nicely complements the crystallographic features reported recently in PbVO3.