Abstract

Hierarchical self-assembly underpins much of the diversity of form and function seen in soft systems,
yet the pathways by which they achieve their final form are not always straightforward –
intermediate steps, kinetic effects and finite sizes of aggregates all influence the self-assembly pathways
of these systems. In this paper, we use molecular dynamics simulations of binary mixtures of
spheres and ellipsoidal discs to investigate the self-assembly of anisotropic aggregates with internal
structures. Through this, the full aggregation pathways of spontaneously chiral, multi-bilayer
and multi-layer assemblies have been tracked and characterised via a semi-qualitative analysis. This
includes the unambiguous identification of first-, second- and third-generation hierarchical assemblies
within a single simulation. Given the significant challenge of tracking full aggregation pathways
in experimental systems, our findings strongly support the notion that molecular simulation has
much to contribute to improving our understanding of hierarchical self-assembling systems.