Structure, stability, absorption spectra and aromaticity of the singly and doubly silicon doped aluminum clusters AlnSim0/+ with n = 3–16 and m = 1, 2

Structures of the binary AlnSim clusters in both neutral and cationic states were investigated using DFT and TD-DFT (B3LYP/6-311+G(d)) and (U)CCSD(T)/cc-pvTZ calculations. Silicon-doped aluminum clusters are characterized by low spin ground states. For small sizes, the Si dopant prefers to be located at vertices having many edges. For larger sizes, the Si atom prefers to be endohedrally doped inside an Aln cage. Relative stability, adiabatic ionization energy and dissociation energies of each cluster size were evaluated. A characteristic of most Si doped Al clusters is the energetic degeneracy of two lowest-lying isomers. Calculated results confirm the high stability of the sizes Al4Si2, Al12Si and Al11Si2+ as “magic” clusters, that exhibit 20 or 40 shell electrons and are thermodynamically more stable as compared to their neighbors. Electronic absorption spectra of isoelectronic magic clusters Al13−, Al12Si, and Al11Si2+ that have two pronounced bands corresponding to blue and violet lights, have been rationalized by using the electron shell model. The magnetically included ring current density (MICD) analyses suggest that they are also aromatic structures as a result of the “magic” 40 shell electrons.