The
singular properties of nanoparticles have awaked great interest in both the
scientific and technological communities, and the size dependence of their
thermodynamic properties has been a hot topic of research in recent years. The
surface energy, related to the energetic difference between a surface atom and
a bulk one, is one of the basic quantities that can be used to understand
surface structures, reconstructions, roughening and relaxations.
Following
the framework established by Hill and Chamberlin to analyze the extension of
thermodynamics of small systems to metastable states, we attempt a statistical
mechanic approach to our previous thermodynamic analysis of electrochemical
formation of core-shell nanoparticles. A brief discussion on the model is made
illustrating its application with computer simulation using realistic
interatomic potentials.
The
behavior of those systems where the binding energy of the adsorbate to the
substrate is more positive than that of the bulk adsorbate showed close
similarities to that of the classical behavior expected of the growth of pure
metal clusters. However, when the adsorbate/substrate interaction is stronger
than the bulk adsorbate interaction, a manifold of behavior arise depending on
cluster size and shape.
