The effect of combined roundness and polydispersity on the phase behavior of hard-rectangle fluids

TL;DR

This study models polydisperse rounded hard rectangles to analyze how roundness and polydispersity influence phase transitions, revealing effects on tetratic stability, phase transition order, and phase fractionation.

Contribution

It introduces a scaled particle theory model for polydisperse rounded hard rectangles and explores how roundness and polydispersity affect phase behavior and transitions.

Findings

Roundness reduces tetratic phase stability.

Polydispersity causes phase fractionation, enriching nematic phase with lower roundness particles.

High polydispersity can change the isotropic-nematic transition from second to first order.

Abstract

We introduce a model for a fluid of polydisperse rounded hard rectangles where the length and width of the rectangular core are fixed, while the roundness is taken into account by the convex envelope of a disk displaced along the perimeter of the core. The diameter of the disk has a continuous polydispersity described by a Schultz distribution function. We implemented the scaled particle theory for this model with the aim to studying: (i) the effect of roundness on the phase behavior of the one-component hard-rectangle fluid, and (ii) how polydispersity affects phase transitions between isotropic, nematic and tetratic phases. We found that roundness greatly affects the tetratic phase, whose region of stability in the phase diagram strongly decreases as the roundness parameter is increased. Also the interval of aspect ratios where the tetratic-nematic and isotropic-nematic phase transitions are of first order considerably reduces with roundness, both transitions becoming weaker. Polydispersity induces strong fractionation between the coexisting phases, with the nematic phase enriched in particles of lower roundness. Finally, for high enough polydispersity and certain mean aspect ratios, the isotropic-to-nematic transition can change from second (for the one-component fluid) to first order. We also found a packing-fraction inversion phenomenon for large polydispersities: the coexisting isotropic phase has a higher packing fraction than the nematic.