A Molecular Dynamics Study of The Translation and Rotation of Amphiphilic Janus Nanoparticles at a Vapor-Liquid Surface

TL;DR

This study uses molecular dynamics simulations to investigate how heterogeneity affects the behavior of Janus nanospheres at vapor-liquid interfaces, revealing velocity-dependent tilt and drag characteristics that influence particle dynamics.

Contribution

It introduces a detailed MD-based free energy landscape for Janus nanoparticles at interfaces, highlighting the effects of heterogeneity and thermal fluctuations on their motion.

Findings

Janus particles exhibit velocity-dependent tilt at interfaces.

Drag force remains below the fully immersed value.

Different orientations lead to apparent violations of Stokes-Einstein relation.

Abstract

We study the effects of heterogeneity on interfacial pinning and hydrodynamic drag using molecular dynamics (MD) simulations of Janus nanospheres at a liquid/vapor interface. We construct the free energy landscape for this system, both in the continuum approximation using surfaces tensions and the flat-interface approximation and atomistically using MD and thermodynamic integration. The results of the two methods differ in detail due to interfacial distortion and finite width, as well as thermal fluctuations, and only the MD landscape is consistent with simulations of a nanosphere approaching the interface from the liquid or vapor side. When dragged along an interface, these Janus particles exhibit a velocity-dependent tilt accompanied by a weak variation in drag force, but never an enhancement of the drag force beyond the value when fully immersed. This velocity dependence arises when the interface is pinned at heterogeneities and prevents the particle from rotating, and similar behavior is observed for homogeneous but non-spherical particles. The occurrence of different particle orientations having different drag coefficients may lead to an apparent violation of the Stokes-Einstein relation.