Leveraging Curvature to Drive Non-Trivial Corona Morphologies for Anisotropic Particles*

Nanoparticles can self-assemble into materials with unique optical, electronic, and thermal properties if their shape and interactions are judiciously designed. Previous theoretical works that consider how the shape of the ligand shell around a nanoparticle affects interparticle interactions have successfully predicted experimentally realized assemblies [1]. Here we simulate nanoparticles with a range of core shapes and with ligand shells whose shape varies with the number and length of the ligands as well as with core shape. We focus our study on designing ligand-grafted nanoparticles that are experimentally realizable today but whose synthesis and assembly have not yet been reported. We find that the partitioning of ligands to high curvature regions of the nanoparticle core is a primary driver for effective shape, resulting in nontrivial ligand shell morphologies that we are able to self-assemble into novel structures in hard particle monte carlo simulations. Our findings may help to guide future design and synthesis of nanoparticles for self-assembly.

[1] Elbert, K. C., Zygmunt, W., Vo, T., Vara, C. M., Rosen, D. J., Krook, N. M., Glotzer, S. C., & Murray, C. B. (2021). Science Advances, 7(23), eabf9402.