Photoelectron spectra of Al-n(-) (n = 2-20) clusters are presented. Du
e to the improved energy resolution and the relatively high photon ene
rgy (h nu = 6.424 eV, ArF laser radiation) available in our experiment
the spectra reveal the mechanism of the onset of the s-p hybridizatio
n occuring in these particles. Between Al-6(-)-Al-12(-) a mixing of th
e uppermost antibonding 3s derived orbital with the 3p band takes plac
e which is observed simultaneously with the 2D-->3D structural transit
ion predicted for Al clusters in this size range. Starting from Al-13(
-) a pattern resembling an electronic shell structure is identified.