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.