Isomorphs in nanoconfined liquids

TL;DR

This paper investigates whether Roskilde-simple liquids exhibit isomorphs under nanoconfinement, demonstrating through simulations that their structure and dynamics remain invariant along these curves even with inhomogeneous density profiles.

Contribution

The study extends the concept of isomorphs to nanoconfined liquids, showing they approximately hold in slit-pore geometries with inhomogeneous densities, which was previously unconfirmed.

Findings

Good scaling of density profiles along isomorphs

Invariant mean-square displacements in simulations

Supports potential experimental observation in confined systems

Abstract

We study in this paper the possible existence of Roskilde-simple liquids and their isomorphs in a rough-wall nanoconfinement. Isomorphs are curves in the thermodynamic phase diagram along which structure and dynamics are invariant in suitable nondimensionalized units. Two model liquids using molecular dynamics computer simulations are considered: the single-component Lennard-Jones (LJ) liquid and the Kob-Andersen binary LJ mixture, both of which in the bulk phases are known to have isomorphs. Nanoconfinement is implemented by adopting a slit-pore geometry with fcc crystalline walls; this implies inhomogenous density profiles both parallel and perpendicular to the confining walls. Despite this fact and consistent with an earlier study [Ingebrigtsen et. al, Phys. Rev. Lett. 111, 235901 (2013)] we find that these nanoconfined liquids have isomorphs to a good approximation. More specifically, we show good scaling of inhomogenous density profiles, mean-square displacements, and higher-order structures probed using the topological cluster classification algorithm along the isomorphs. From this study, we conjecture that in experiments, Roskilde-simple liquids may exhibit isomorphs if confined in a suitable manner, for example with carbon nanotubes. Our study thus provides an alternative framework for understanding nanoconfined liquids.