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Stability and Reactivity of Silicon Magic Numbers Doped with Aluminum and Phosphorus Atoms.

The progressive scaling down of the silicon-based electronics has allowed to develop devices at nanometer scale, requiring new engineering techniques guided by fundamental chemical and physical concepts. Particularly, the nanostructured cluster systems are promising materials since their physical-chemical properties are sensitive to its shape, size, and chemical components, such that completely different materials can be produced by the simple addition or removal of a single atom. These size-tunable properties can open a new area in materials science and engineering. In the present work, quantum chemical methods were used to study the chemical substitution effects caused by subvalent (aluminum) and supervalent (phosphorus) atoms in the physical-chemical properties of some small silicon clusters, which demonstrate high stability, called magic numbers. The changes in the electronic structure and chemical acceptance to the dopants were evaluated with respect to ionization potential, electronic excitation energy, stability, and reactivity parameters. Taken together, these results enable to identify the most stable silicon-doped clusters. Regarding electrophilic reactions, Si10P is the most favorable system, while for nucleophilic reactions, none of the doped clusters resulted in higher stability.