Electronic structures of Al–Si clusters and the magic number structure Al₈Si₄

The low-energy structures of Al₈Si_m (m = 1–6) have been determined by using the genetic algorithm combined with density functional theory and the Second-order Moller-Plesset perturbation theory (MP2) models. The results show that the close-packed structures are preferable in energy for Al–Si clusters and in most cases there exist a few isomers with close energies. The valence molecular orbitals, the orbital level structures and the electron localisation function (ELF) consistently demonstrate that the electronic structures of Al–Si clusters can be described by the jellium model. Al₈Si₄ corresponds to a magic number structure with pronounced stability and large energy gap; the 40 valence electrons form closed 1S²1P⁶1D¹⁰2S²1F¹⁴2P⁶ shells. The ELF attractors also suggest weak covalent Si–Si, Si–Al and Al–Al bonding, and doping Si in aluminium clusters promotes the covalent interaction between Al atoms.