Anomalous behavior and structure of a liquid of particles interacting through the harmonic-repulsive pair potential near the crystallization transition

TL;DR

This study investigates the complex behavior of a soft matter model with harmonic-repulsive interactions, revealing unusual properties like negative thermal expansion and structural rearrangements near crystallization, with implications for understanding ultrasoft systems.

Contribution

It demonstrates that simple one-length-scale ultrasoft interactions can produce complex fluid behaviors and structural phenomena typically associated with multi-scale interactions.

Findings

Liquid exhibits negative thermal expansion at certain pressures.

Crystallization can increase volume and potential energy.

High stability against crystallization observed at specific pressures.

Abstract

A characteristic property of many soft matter systems is an ultrasoft effective interaction between their structural units. This softness often leads to complex behavior. In particular, ultrasoft systems under pressure demonstrate polymorphism of complex crystal and quasicrystal structures. Therefore, it is of interest to investigate how different can be the structure of the fluid state in such systems at different pressures. Here we address this issue for the model liquid composed of particles interacting through the harmonic-repulsive pair potential. This system can form different crystal structures as the liquid is cooled. We find that, at certain pressures, the liquid exhibits unusual properties, such as the negative thermal expansion coefficient. Besides, the volume and the potential energy of the system can increase during crystallization. At certain pressures, the system demonstrates high stability against crystallization and it is hardly possible to crystallize it on the timescales of the simulations. To address the liquid's structure at high pressures, we consider the scaled pair distribution function (PDF) and the bond-orientational order (BOO) parameters. The marked change happening with the PDF, as pressure increases, is the splitting of the first peak which is caused by the appearance of non-negligible interaction with the second neighbors and the following rearrangement of the structure. Our findings suggest that non-trivial effects, usually explained by different interactions at different spatial scales, can be observed also in one-component systems with simple one-length-scale ultrasoft repulsive interactions.