The emergence of bulk structure in clusters via isotropic multi-well pair potentials

TL;DR

This study explores how bulk structures emerge in finite clusters of soft materials using multi-well isotropic pair potentials, revealing size-dependent structural transitions influenced by interaction details.

Contribution

It demonstrates how multi-well pair potentials can be used to understand and control the emergence of non-close packings in finite clusters, advancing material design strategies.

Findings

Small clusters tend to form close-packed structures regardless of bulk preferences.

The size at which bulk structure appears depends on coordination number and potential shape.

Anisotropic structures emerge at larger sizes through secondary bonding interactions.

Abstract

The mechanical, optical, and chemical properties of a wide variety of soft materials are enabled and constrained by their bulk structure. How this structure emerges at small system sizes during self-assembly has been the subject of decades of research, with the aim of designing and controlling material functionality. Despite these efforts, it is still not fundamentally understood how nontrivial interparticle interactions in a finite $N$-body system influence resultant structure, and how that structure depends on $N$. In this study, we investigate the emergence of non-close packings using multi-well isotropic pair potentials to simulate finite cluster formation of four distinct two-dimensional crystal structures. These pair potentials encode multiple preferred length scales into the system, allowing us to understand how anisotropic structural motifs -- as opposed to close-packing -- emerge as cluster size $N$ increases. We find a tendency toward close-packing at small system sizes irrespective of the bulk structure; however, the system size at which bulk structure emerges is influenced by the coordination number of the bulk and the shape of the pair potential. Anisotropic structure emerges through the formation of bonds at a secondary bonding length at larger system sizes, and it is also dependent upon the shape of the pair potential. Our findings demonstrate that tuning particle-particle interactions can enable the engineering of nano- or mesoscale soft matter clusters, in applications as diverse as drug delivery and hierarchical materials design.