Free Energy Landscape of Colloidal Clusters in Spherical Confinement.

The structure of finite self-assembling systems depends sensitively on the number of constituent building blocks. Recently, it was demonstrated that hard sphere-like colloidal particles show a magic number effect when confined in spherical emulsion droplets. Geometric construction rules permit a few dozen magic numbers that correspond to a discrete series of completely filled concentric icosahedral shells. Here, we investigate the free energy landscape of these colloidal clusters as a function of the number of their constituent building blocks for system sizes up to several thousand particles. We find that minima in the free energy landscape, arising from the presence of filled, concentric shells, are significantly broadened. In contrast to their atomic analogues, colloidal clusters in spherical confinement can flexibly accommodate excess colloids by ordering icosahedrally in the cluster center while changing the structure near the cluster surface. In-between these magic number regions, the building blocks cannot arrange into filled shells. Instead, we observe that defects accumulate in a single wedge and therefore only affect a few tetrahedral grains of the cluster. We predict the existence of this wedge by simulation and confirm its presence in experiment using electron tomography. The introduction of the wedge minimizes the free energy penalty by confining defects to small regions within the cluster. In addition, the remaining ordered tetrahedral grains can relax internal strain by breaking icosahedral symmetry. Our findings demonstrate how multiple defect mechanisms collude to form the complex free energy landscape of hard sphere-like colloidal clusters.