Probing the Structures, Stabilities and Electronic Properties of Neutral and Anionic PrSinλ (n = 1–9, λ = 0, − 1) Clusters: Comparison with Pure Silicon Clusters

Silicon-based clusters have attracted particular attention because they are regard as building blocks for developing silicon-based nanomaterials. However, pure silicon clusters have low chemical stability owing to their dangling bonds. Doping with lanthanide atoms is a good way to form closed-shell of M@Sin clusters and alter their electronic and magnetic properties. Here, we systematically study the lanthanide element Pr doped neutral and anionic silicon clusters by using density functional theory. Extensive searches for ground-state structures of Sin+1λ and PrSinλ (n = 1–9, λ = 0, − 1) clusters were carried out based on the comparison between experimental photoelectron spectroscopy and simulated spectra. Furthermore, the calculated AEA values of our obtained structures show good agreement with the experimental values. Based on averaged binding energies, fragmentation energies and HOMO–LUMO gaps, their relative stabilities were analyzed. Furthermore, the patterns of HOMOs for the most stable isomers were investigated to gain insight into the nature of bonding. The results show that some σ-type and few π-type bonds are formed among Si and Pr atoms. To achieve a insight into localization of charge and charge-transfer information, the Mulliken population are analyzed and discussed.