A Criterion for the Formation of Nonequilibrium Self-Assembled Structures.

Is there a criterion able to determine the type of structures formed in a nonequilibrium self-assembly process? This important question has a clear answer when the process takes place under equilibrium conditions: structures emerge at minimum values of the free energy. Experiments, however, have shown that when self-assembly takes place outside equilibrium, they do not appear at those free energy minima but rather at optimal values of structural parameters. On the basis of these observations, we propose a selection criterion for which structures come up at the minima of a nonequilibrium free energy that takes into account the energy needed to change their configuration. The criterion is able to predict the formation and configuration of structures such as Liesegang rings and patterns in magnetic colloids and could constitute a powerful tool to understand the synthesis of advanced materials, enantiomers, and nanoparticles.