Soft repulsive interactions, particle rearrangements and size selection in the self-assembly of nanoparticles at liquid interfaces

Abstract

In the adsorption of nanoparticles at liquid interfaces, soft and short ranged repulsive effective interactions between the nanoparticles at the interface may eventually induce crowding, slow dynamics and jamming at high surface coverage. These phenomena can interfere during the adsorption process, significantly slowing down its kinetics. Here, by means of numerical simulations, we find that modifying the effective interactions, which can be achieved for example by grafting differently functionalized polymer shells on the bare nanoparticles, may qualitatively change such interplay. In particular our results suggest that, in the presence of ultrasoft particle interactions such as the ones described by a Gaussian Core Model potential, a small size polydispersity can be sufficient to decouple the adsorption kinetics from the slow dynamics that develops at the interface, due to a qualitative change from an irreversible adsorption controlled by particle rearrangements at the interface to one dominated by size selection mechanisms. These findings may be useful to achieve higher surface coverages and faster adsorption kinetics.