Structure and equation of state of interaction site models for disc-shaped lamellar colloids

TL;DR

This study uses RISM and PRISM theories to model the structure and equation of state of lamellar colloids, showing good agreement with simulations and revealing universal behavior when scaled appropriately.

Contribution

It demonstrates that PRISM, a simpler theory, effectively predicts colloid behavior when using correct form factors, and clarifies the impact of modeling choices on the equation of state.

Findings

PRISM yields accurate results with correct form factors.

Equation of state saturates with increasing number of sites.

Scaled equations of state collapse onto a master curve.

Abstract

We apply RISM (Reference Interaction Site Model) and PRISM (polymer-RISM) theories to calculate the site-site pair structure and the osmotic equation of state of suspensions of circular or hexagonal platelets (lamellar colloids) over a range of ratios of the particle diameter over thickness. Despite the neglect of edge effects, the simpler PRISM theory yields results in good agreement with the more elaborate RISM calculations, provided the correct form factor, characterizing the intramolecular structure of the platelets, is used. The RISM equation of state is sensitive to the number of sites used to model the platelets, but saturates when the hard spheres, associated with the interaction sites, nearly touch; the limiting equation of state agrees reasonably well with available simulation data for all densities up to the isotropic-nematic transition. When properly scaled with the second virial coefficient, the equations of state of platelets with different aspect ratios nearly collapse on a single master curve.