The Devil is in the details: Pentagonal bipyramids and dynamic arrest

TL;DR

This study evaluates pentagonal bipyramid structures as a detailed order parameter for understanding vitrification in colloidal suspensions, revealing dynamic correlations and continuous growth with volume fraction.

Contribution

It introduces pentagonal bipyramid membership as a novel, finer structural order parameter for analyzing the glass transition in colloids, complementing existing methods.

Findings

Pentagonal bipyramid membership correlates with large particle displacements.

It continues to increase with volume fraction, unlike icosahedral structures.

Provides insights into local structural dynamics during vitrification.

Abstract

Colloidal suspensions have long been studied as a model for atomic and molecular systems, due to the ability to fluorescently label and individually track each particle, yielding particle-resolved structural information. This allows various local order parameters to be probed that are otherwise inaccessible for a comparable molecular system. For phase transitions such as crystallisation, appropriate order parameters which emphasise 6-fold symmetry are a natural choice, but for vitrification the choice of order parameter is less clear cut. Previous work has highlighted the importance of icosahedral local structure as the glass transition is approached. However, counting icosahedra or related motifs is not a continuous order parameter in the same way as, for example, the bond-orientational order parameters $Q_{6}$ and $W_6$. In this work we investigate the suitability of using pentagonal bipyramid membership, a structure which can be assembled into larger, five-fold symmetric structures, as a finer order parameter to investigate the glass transition. We explore various structural and dynamic properties and show that this new approach produces many of the same findings as simple icosahedral membership, but we also find that large instantaneous displacements are often correlated with significant changes in pentagonal bipyramid membership, and unlike the population of defective icosahedra, the pentagonal bypyramid membership and spindle number do not saturate for any measured volume fraction, but continues to increase.