Targeted Discovery of Low-Coordinated Crystal Structures via Tunable Particle Interactions

Particles interacting via isotropic, multiwell pair potentials have been shown to self-assemble into a range of crystal structures, yet how the characteristics of the underlying interaction potential give rise to the resultant structure remains largely unknown. We have thus developed a functional form for the interaction potential in which all features can be tuned independently. We perform continuous parameter space searches by systematically changing pairs of parameters, controlling the various features of the interaction potential. By enforcing a repulsive first well (controlling particle interactions of the first neighbor shell), we stimulate the formation of low-coordinated assemblies. We report the self-assembly of 20 previously unknown crystal structure types, 14 of which have low coordination numbers. Despite limiting the search to a small region of the vast parameter space of possible particle interactions, a wealth of complexity and symmetry is apparent within these crystal structures, which include clathrates with empty cages and low-symmetry structures. Our findings suggest that an unknown number of previously undiscovered crystal structure configurations are possible through self-assembly, which can serve as interesting design targets for soft condensed matter synthesis.