The reactivity of aluminum clusters as a function of atom number

This work is directed towards an effort to understand clusters as superatoms. A perspective of the field is presented in Chapter 1. Experimental methods are described in Chapter 2 including a detailed hardware specification of the fast-flow reactor. In Chapter 3, the combined results of two studies of the formation and oxygen etching of AlnHm - clusters are presented. The origin of resistance to oxygen etching is discussed as a result of the conservation of electronic spin angular momentum. In Chapter 4, the size-dependent reactivity of aluminum cluster anions with water is presented and attributed to the dissociative chemisorption of water molecules at identified surface sites. The relative reactivity is shown to be dependent on geometric structure rather than the more commonly considered electronic shell structure.