Publication Date

11-12-2025

Document Type

Article

Publication Title

The Journal of Chemical Physics

Volume

163

Issue

18

DOI

10.1063/5.0298519

Abstract

A multispecies diffuse interface model is formulated in a fluctuating hydrodynamics framework for the purpose of simulating surfactant interfaces at the nanoscale. The model generalizes previous work to ternary mixtures, employing a Cahn–Hilliard free energy density combined with incompressible, isothermal fluctuating hydrodynamics where dissipative fluxes include both deterministic and stochastic terms. The intermolecular parameters in the free energy are chosen such that one species acts as a partially miscible surfactant. From Laplace pressure measurements, we show that in this model the surface tension decreases linearly with surfactant concentration, leading to Marangoni convection for interfaces with concentration gradients. In the capillary wave spectrum for interfaces with and without surfactant, we find that for the former, the spectrum deviates significantly from classical capillary wave theory, presumably due to Gibbs elasticity. In non-equilibrium simulations of the Rayleigh–Plateau instability, deterministic simulations showed that the surfactant delays pinching of a fluid cylinder into droplets. However, stochastic simulations indicate that thermal fluctuations disrupt the surfactant’s stabilizing effect. Similarly, the spreading of a patch of surfactant, driven by Marangoni convection, was found to be partially suppressed by thermal fluctuations.

Keywords

Thermal fluctuations, Surfactants, Interfacial tension, Hydrodynamics, Capillary waves, Stochastic processes

Comments

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in The Journal of Chemical Physics, Volume 163, Issue 18, Article 184104 , 2025 and may be found at https://doi.org/10.1063/5.0298519.

Department

Physics and Astronomy

Available for download on Thursday, November 12, 2026

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