Hidden geometries in networks arising from cooperative self-assembly

TL;DR

This paper introduces a computational model for cooperative self-assembly of structured particle groups into networks, revealing how geometry and chemical affinity influence large-scale structure formation and complexity.

Contribution

The study presents a novel model combining geometric rules and chemical affinity to simulate multilevel self-assembly with simplices, analyzed through graph theory and topology.

Findings

Higher Q-connectedness can arise from geometric factors alone.

Chemical potential and polydispersity modulate network structure.

Networks of mono-dispersed simplices resemble quantum and chemical clusters.

Abstract

Multilevel self-assembly involving small structured groups of nano-particles provides new routes to development of functional materials with a sophisticated architecture. Apart from the inter-particle forces, the geometrical shapes and compatibility of the building blocks are decisive factors in each phase of growth. Therefore, a comprehensive understanding of these processes is essential for the design of large assemblies of desired properties. Here, we introduce a computational model for cooperative self-assembly with simultaneous attachment of structured groups of particles, which can be described by simplexes (connected pairs, triangles, tetrahedrons and higher order cliques) to a growing network, starting from a small seed. The model incorporates geometric rules that provide suitable nesting spaces for the new group and the chemical affinity $\nu$ of the system to accepting an excess number of particles. For varying chemical affinity, we grow different classes of assemblies by binding the cliques of distributed sizes. Furthermore, to characterise the emergent large-scale structures, we use the metrics of graph theory and algebraic topology of graphs, and 4-point test for the intrinsic hyperbolicity of the networks. Our results show that higher Q-connectedness of the appearing simplicial complexes can arise due to only geometrical factors, i.e., for $\nu = 0$, and that it can be effectively modulated by changing the chemical potential and the polydispersity of the size of binding simplexes. For certain parameters in the model we obtain networks of mono-dispersed clicks, triangles and tetrahedrons, which represent the geometrical descriptors that are relevant in quantum physics and frequently occurring chemical clusters.