Valence-band hybridization in sulphides

Abstract

The hybridization state in solids often defines the critical chemical and physical properties of a compound. However, it is difficult to spectroscopically detect and evaluate hybridization beyond just general fingerprint signatures. Here, the valence-band hybridization of metal d-derived bands (short: “metal d bands”) in selected metal sulphides is studied with a combined spectroscopic and theoretical approach to derive deeper insights into the fundamental nature of such compounds. The valence bands of the studied sulphides are comprised of hybrid bands derived from the metal d, S 3s, and S 3p states. Employing S K and L 2,3 X-ray emission spectroscopy and spectra calculations based on density functional theory, the degree of hybridization (i.e., the covalency) of these bands can be directly probed as a function of their relative energies. We find that the relative intensity of the “metal d band” features in the spectra scales with the inverse square of the energy separation to the respective sulfur-derived bands, which can be analytically derived from a simple two-orbital model. This study demonstrates that soft X-ray emission spectroscopy is a powerful tool to study valence state hybridization, in particular in combination with hard X-ray emission spectroscopy, promising a broad impact in many research fields.