Role of Cluster Geometry in Evolution of Electronic Structures of Small Aluminum Clusters

The electronic structures of small aluminum clusters,Al_(n)(n=5-24),are investigated by a localized-orbital theory based on the tight-binding approximation.Magic-numbered clusters each exhibit a HOMO-LUMO gap maximum,and simultaneously an s-p gap minimum,but not necessarily an ionization potential maximum,where HOMO-LUMO gap denotes the energy gap between the highest occupied orbital and the lowest unoccupied orbital of the cluster.Also revealed is an irregular odd-even alternation in HOMO-LUMO gaps for Al_(n)(n=7-24).Cluster geometry either contributes to or dominates these findings.