Redefining the Mechanism of O₂ Etching of Al_n^– Superatoms: An Early Barrier Controls Reactivity, Analogous to Surface Oxidation

New insights into aluminum anion cluster reactivity with O₂ were obtained through temperature-dependent kinetics measurements. Overall reactivity is controlled by a barrier at an avoided crossing where charge is transferred from the cluster to the O₂, mechanistically similar to what occurs as O₂ approaches a bulk Al surface. Contrary to prior interpretations, spin conservation does not inhibit the reaction of clusters with an odd number of Al atoms. In fact, the only spin constraint in these systems is on the reactivity of even clusters due to repulsive surfaces, not previously recognized. Although the superatom nature of Al₁₃^– is manifest in its high electron binding energy (EBE), the mechanism of its reactivity is not special; it reacts with O₂ as if it were a small piece of bulk Al. These experiments highlight the sensitivity of Al cluster reactivity with O₂ to temperature and EBE, uncovering routes to industrial scale use of aluminum superatom-based materials.