Evolution of local electronic structure in alabandite and niningerite solid solutions [(Mn,Fe)S, (Mg,Mn)S, (Mg,Fe)S] using sulfur K- and L-edge XANES spectroscopy

摘要

Synchrotron radiation S K- and L-edge X-ray absorption near-edge structure (XANES) spectra are reported for the cubic, rocksalt (B1) structure sulfides niningerite (MgS), alabandite (MnS), and oldhamite (CaS), and for their solid solutions (Mn,Fe)S and (Mg,Mn)S, and S L-edge XANES spectra are reported also for (Mg,Fe)S solid solutions. Pre-edge features at the S K-edge are attributed to transition of S 1s electrons to the lowest available unoccupied S 3p * antibonding states hybridized with metal 3d(e_g) states, and at the S L-edge to transition of S 2p electrons to unoccupied S 3s *, 4s *, and 3d antibonding states hybridized with metal 3d(e_g) states, and to a lesser extent 3d(t_2g) states.