Diffusion, density, and defects on spheres.

We simulate and model diffusion of spherical colloids of radius, a , on spherical surfaces of radius, R , as a function of relative size and surface concentration. Using Brownian dynamics simulations, we quantify diffusion and microstructure at different concentrations ranging from single particles to dense crystalline states. Self-diffusion and structural metrics (pair distribution, local density, and topological charge) are indistinguishable between spheres and planes for all concentrations up to dense liquid states. For concentrations approaching and greater than the freezing transition, smaller spheres with higher curvature show increased diffusivities and nonuniform density/topological defect distributions, which differ qualitatively from planar surfaces. The total topological charge varies quadratically with sphere radius for dense liquid states and linearly with sphere radius for dense crystals with icosahedrally organized grain scars. Between the dense liquid and dense crystal states on spherical surfaces is a regime of fluctuating and interacting defect clusters. We show local density governs self-diffusion in dense liquids on flat and spherical surfaces via the pair distribution. In contrast, dynamic topological defects couple to finite diffusivities through freezing and in low density crystal states on spherical surfaces, where neither exist on flat surfaces.