Shape‐Driven Colloidal Crystal—Crystal Transitions

Recent experimental, theoretical, and computational work has shown that anisotropic colloids exhibit a rich phase behavior, including the self‐assembly of complex crystal phases. Here, we study the thermodynamics of crystal—crystal transitions that are driven by changes in colloid shape. Using rare event sampling techniques, we find that shape‐driven crystal—crystal transitions that have similar diffusionless pathways can have unexpectedly complex thermodynamic behaviors. We discuss implications of our results for reconfigurable colloidal materials.