Shape control of deformable charge-patterned nanoparticles

Abstract

Deformable nanoparticles (NPs) offer unprecedented opportunities as dynamic building blocks that can spontaneously reconfigure during assembly in response to environmental cues. Designing reconfigurable materials based on deformable NPs hinges on an understanding of the shapes that can be engineered in these NPs. We solve for the low-energy shapes of charge-patterned deformable NPs by using molecular dynamics-based simulated annealing to minimize a coarse-grained model Hamiltonian characterized with NP elastic and electrostatic energies subject to a volume constraint. We show that deformable spherical NPs of radius 50 nm whose surface is tailored with octahedrally distributed charged patches and double-cap charged patches adapt their shape differently in response to changes in surface charge coverage and ionic strength. We find shape transitions to rounded octahedra, faceted octahedra, faceted bowls, oblate spheroids, spherocylinders, dented beans, and dimpled rounded bowls. We demonstrate that similar shape transitions can be achieved in deformable NPs of different sizes. The effects of counterion condensation on the free-energetic drive associated with the observed deformations are examined via Manning model calculations that utilize simulation-derived estimates for the NP Coulomb energy under salt-free conditions. The charge-pattern-based shape control of deformable NPs has implications for the design of responsive nanocontainers and for assembling reconfigurable materials whose functionality hinges on the shape-shifting properties of their nanoscale building blocks.