Connections between resonant inelastic x-ray scattering and complementary x-ray spectroscopies: probing excitons at Al K and L$_1$ edges of $\alpha$-Al$_2$O$_3$

TL;DR

This study uses ab initio calculations to explore excitonic effects in Al2O3 at Al K and L1 edges, linking X-ray absorption, Raman spectroscopy, and RIXS, and predicting spectra beyond current experimental data.

Contribution

It provides a comprehensive theoretical analysis of excitonic effects in Al2O3 across multiple X-ray spectroscopies, including new RIXS predictions at different photon energies.

Findings

Excellent agreement between calculated and experimental spectra at Al K and L1 edges.

Identification of two regimes in RIXS spectra: Raman-like below threshold and fluorescence above.

Prediction of RIXS spectra features beyond independent-particle approximation.

Abstract

We present an ab initio study of neutral core and valence electronic excitations in {\alpha}-Al2O3 by solving the Bethe-Salpeter equation (BSE) of many-body perturbation theory within an all-electron framework. Calculated spectra at the Al K and L1 edges are in remarkable agreement with available experiments from X-ray absorption (XAS) and X-ray Raman spectroscopy once excitonic effects are taken into account. The combination of the BSE spectra for the two techniques confirms the dipole-forbidden nature of the exciton prepeak as suggested by recent calculations based on density-functional theory. Moreover, we make predictions for resonant inelastic X-ray scattering (RIXS) spectra at K and L1 edges, which strikingly fully overlap also beyond an independent-particle picture. The RIXS calculations reveal two distinct regimes as a function of incoming photon energy. Below and at the XAS threshold, we observe Raman-like features, characterised by strong excitonic effects, which we directly compare to peaks in the loss function. Above the XAS threshold, instead, fluorescence features become predominant: RIXS spectra can be well described and analyzed within an independent-particle approximation showing similarity with the X-ray emission spectrum.