K-edge XANES of octahedral aluminum compounds: similarities and differences via the analysis of excitonic properties

TL;DR

This paper uses ab initio calculations to analyze and compare the XANES spectra at the aluminum K edge for three octahedral aluminum compounds, revealing how excitonic effects influence spectral features.

Contribution

It provides a detailed analysis of excitonic effects on Al K-edge XANES spectra in different compounds using the Bethe-Salpeter equation approach.

Findings

Significant spectral differences among Al$_2$O$_3$, AlF$_3$, and AlCl$_3$

Excitonic effects strongly modify spectral features, including the suppression of the pre-peak in AlCl$_3$

Spectral variations are linked to the compounds' band structures and excitonic properties.

Abstract

This study presents an \textit{ab initio} investigation of the XANES spectra at the aluminum K edge for three compounds: Al$_2$O$_3$, AlF$_3$ and AlCl$_3$, where the Al atoms share the same oxidation state~(III) and are coordinated in an octahedral symmetry. The XANES spectra calculated within the independent-particle approximation reveal significant differences, including shifts in the spectrum onset, variations in the spectral shapes, and the presence of a pre-peak in the case of AlCl$_3$, all in correspondence with the behavior of the PDOS of the absorbing atom in the different materials. The origin of the features stems from the specific band structure of each compound. When electron--hole interactions are taken into account through the solution of the Bethe-Salpeter equation, a series of dark and bright excitons with large binding energies and Frenkel character is obtained. The strong excitonic effects lead to the suppression of the pre-peak in AlCl$_3$ and further accentuate the differences among the three Al K-edge spectra.