Diffusion, viscosity, and linear rheology of valence-limited disordered fluids

Abstract

We numerically investigate the dynamics and linear rheology of disordered systems made of patchy particles, focusing on the role of valence, temperature, and bonding mechanism. We demonstrate that the dynamics is enslaved to bonding, giving rise to an activated behavior at low temperatures. By independently computing the diffusion constant and the viscosity from the simulations, we also confirm the validity of the Stokes–Einstein relation in valence-limited systems, with two caveats: (i) the diffusion constant requires a finite-size correction, at least at the intermediate density we investigate, and (ii) there is the onset of a breakdown that appears at the lowest temperatures considered. Finally, our results show that the storage and loss moduli of mixtures of divalent and M-valent particles exhibit an apparent power-law dependence on frequency, hinting at the possibility of using the composition to finely tune the rheological response of these materials. Our results compare well with literature experimental data on valence-limited DNA nanostars. In addition, the wealth of data we present and analyze here will help develop and test theoretical frameworks aimed at describing the dynamics of flexible limited-valence particles that self-assemble into disordered networks.