Effect of orientational restriction on monolayers of hard ellipsoids

TL;DR

This study investigates how out-of-plane orientational freedom influences the ordering of monolayers of hard ellipsoids, revealing distinct behaviors for prolate and oblate particles through simulations and theoretical analysis.

Contribution

It introduces a combined Parsons-Lee and Monte Carlo approach to analyze orientational effects in monolayers of ellipsoids, highlighting the contrasting behaviors of prolate and oblate particles.

Findings

Prolate ellipsoids tend to lean out of the plane, destabilizing in-plane order.

Oblate ellipsoids prefer to lean into the plane, enhancing in-plane order.

Out-of-plane freedom significantly alters the phase transition behavior.

Abstract

The effect of out-of-plane orientational freedom on the orientational ordering properties of a monolayer of hard ellipsoids is studied using Parsons-Lee scaling approach and replica exchange Monte Carlo computer simulation. Prolate and oblate ellipsoids exhibit very different ordering properties, namely, the axes of revolution of prolate particles tend to lean out, while those of oblate ones prefer to lean into the confining plane. The driving mechanism of this is that the particles try to maximize the available free area on the confining surface, which can be achieved by minimizing the cross section areas of the particles with the plane. In the lack out-of-plane orientational freedom the monolayer of prolate particles is identical to a two-dimensional hard ellipse system, which undergoes an isotropic-nematic ordering transition with increasing density. With gradually switching on the out-of-plane orientational freedom the prolate particles lean out from the confining plane and a destabilisation of the in-plane isotropic-nematic phase transition is observed. The system of oblate particles behaves oppositely to that of prolates. It corresponds to a two-dimensional system of hard disks in the lack of out-of-plane freedom, while it behaves similar to that of hard ellipses in the freely rotating case.