Photoelectron imaging of small aluminum clusters: quantifying s–p hybridization

Abstract

Photoelectron imaging experiments and detailed calculations are conducted on Al_n⁻ clusters (n = 3–6) and a calibration method is developed for connecting experimental observations of photoelectron angular distributions to theoretical predictions. It is shown that this method can be used to quantify the degree to which the molecular orbitals are built from s- or p-like atomic orbitals. The highest occupied molecular orbitals of these small aluminum clusters are found to contain varying degrees of s–p mixing, with Al₃⁻ containing the “most hybridized” orbital and Al₄⁻ containing the “least hybridized” orbital. It is shown experimentally that s–p hybridization is already present for the trimer species and, similar to other properties of small metal clusters, oscillates with cluster size.