Electronic structure of Gold, Aluminum and Gallium Superatom Complexes

Abstract: Using ab-initio computational techniques on crystal determined clusters, we report on the similarities and differences of Al${50}$(C$_5$(CH$_3)_5){12}$, Ga${23}$(N(Si(CH$_3){3}$)${2}$)${11}$, and Au${102}$(SC$_7$O$_2$H$_5$)${44}$ ligand-protected clusters. Each of the ligand-protected clusters in this study show the similar stable character which can be described via a electronic shell model. We show here that the same type of analysis leads consistently to derive a superatomic electronic counting rule, independently of the metal and ligand compositions. One can define the cluster core as the set of atoms where delocalized single-angular-momentum-character orbitals have hight weight using a combination of Bader analysis and the evaluation of Khon-Sham orbitals. Subsequently one can derive the nature of the ligand-core interaction. These results yield further insight into the superatom analogy for the class of ligand-protected metal clusters.