Connecting Irreversible to Reversible Aggregation: Time and Temperature

TL;DR

This paper demonstrates a formal correlation between elapsed time in irreversible gel formation and equilibrium temperature in reversible aggregation, using molecular dynamics simulations of loopless patchy particles.

Contribution

It introduces a parameter-free model linking irreversible and reversible aggregation processes in loopless branched systems, enhancing understanding of self-assembly kinetics.

Findings

Elapsed time correlates with equilibrium temperature in gel formation.

A parameter-free description of self-assembly kinetics is developed.

Reversible and irreversible aggregation are unified in the same framework.

Abstract

We report molecular dynamics simulations of a gel-forming mixture of ellipsoidal patchy particles with different functionality. We show that in this model, which disfavors the formation of bond-loops, elapsed time during irreversible aggregation -- leading to the formation of an extended network -- can be formally correlated with equilibrium temperature in reversible aggregation. We also show that it is possible to develop a parameter-free description of the self-assembly kinetics, bringing reversible and irreversible aggregation of loopless branched systems to the same level of understanding as equilibrium polymerization.