Local atomic geometry and Ti 1s near-edge spectra in PbTiO$_3$ and SrTiO$_3$

TL;DR

This study combines ab initio molecular dynamics and Bethe-Salpeter calculations to accurately predict Ti 1s near-edge spectra in PbTiO$_3$ and SrTiO$_3$, revealing how local atomic displacements influence spectral features across phase transitions.

Contribution

It introduces a first-principles approach that links local atomic displacements to spectral features, improving the interpretation of near-edge spectra in complex oxides.

Findings

Atomic displacements significantly affect spectral features.

Properly accounting for atomic fluctuations improves spectral predictions.

Spectral evolution with temperature and polarization is well captured.

Abstract

We study Ti 1s near-edge spectroscopy in PbTiO$_3$ at various temperatures above and below its tetragonal-to-cubic phase transition, and in SrTiO$_3$ at room temperature. Ab initio molecular dynamics (AIMD) runs on 80-atom supercells are used to determine the average internal coordinates and their fluctuations. We determine that one vector local order parameter is the dominant contributor to changes in spectral features: the displacement of the Ti ion with respect to its axial O neighbors in each Cartesian direction, as these displacements enhance the cross section for transitions to E$_{\rm g}$-derived core-hole exciton levels. Using periodic five-atom structures whose relative Ti-O displacements match the root-mean-square values from the AIMD simulations, and core-hole Bethe-Salpeter equation (BSE) calculations, we quantitatively predict the respective Ti 1s near-edge spectra. Properly accounting for atomic fluctuations greatly improves the agreement between theoretical and experimental spectra. The evolution of relative strengths of spectral features vs temperature and electric field polarization vector are captured in considerable detail. This work shows that local structure can be characterized from first-principles sufficiently well to aid both the prediction and the interpretation of near-edge spectra