The effect of flexibility and bend angle on the phase diagram of hard colloidal boomerangs

TL;DR

This study investigates how flexibility and bend angle influence the phase behavior of hard semiflexible boomerangs, revealing complex nematic phases and the impact of flexibility on phase stability.

Contribution

It introduces a second-virial theoretical approach to model semiflexible boomerangs, analyzing their orientation distributions and phase diagrams with new insights into biaxial nematic phases.

Findings

Biaxial nematic phase exhibits four-fold symmetry for certain angles.

Flexibility reduces the stability region of the biaxial nematic phase.

Prolate nematic phase becomes more dominant with increased flexibility.

Abstract

We study the effect of flexibility and bend angle on systems of hard semiflexible boomerangs. These are modelled as two rodlike segments joined at one end with an angle that can fluctuate about a preferred angle. We use a second-virial theory for semiflexible chains with two segments, and numerically solve for the full orientation distribution function as a function of the four angles that determine the boomerang's orientation. We plot the single segment distributions as a function of two angles as well as the interarm angle distribution. For stiff boomerangs, we find prolate, oblate, and biaxial nematic phases depending on the bend angle and density, in partial agreement with previous results on rigid boomerangs. For the case that the preferred interarm angle is $90^\circ$, however, we find that the biaxial nematic phase has four-fold rather than two-fold rotational symmetry, and thus requires fourth-rank order parameters to describe it. In addition, we find that flexibility drastically reduces the region of stability for the biaxial nematic phase, with the prolate nematic becoming more favourable.