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

This study presents an ab initio investigation of the XANES spectra at the aluminum $K$ edge for three compounds: ${\mathrm{Al}}_{2}{\mathrm{O}}_{3}, {\mathrm{AlF}}_{3}$, and ${\mathrm{AlCl}}_{3}$, 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 (IPA) reveal significant differences, including shifts in the spectrum onset, variations in the spectral shapes, and the presence of a prepeak in the case of ${\mathrm{AlCl}}_{3}$, all in correspondence with the behavior of the projected density of states of the absorbing atom in the different materials. The origin of those features can, therefore, be identified in 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 prepeak in ${\mathrm{AlCl}}_{3}$ and further accentuate the differences among the three Al $K$-edge spectra, which shows that drawing conclusions solely on the basis of IPA spectra may be misleading.