Nucleation and superstabilization in small systems

Phase transitions are known to present peculiarities in small systems that are related to depletion effects of the ambient phase. Mass conservation affects the conditions of thermodynamic equilibrium between a nucleus of the new phase and the matrix as compared with nucleation in infinite systems. This finite-size effect is known to delay the phase transition but can also impede nucleation in very small systems as it stabilizes the initial state, originally metastable in infinite systems. In this work, we investigate this superstabilization effect in the context of classical nucleation theory in multicomponent solutions and we derive an analytical expression for the system size below which nucleation becomes thermodynamically impossible. Comparing with the exact solution, our simple result is shown to accurately predict the superstabilization effect, and can therefore be used, for instance, as a guideline for the design of novel nanomaterials.