A many-body dissipative particle dynamics parametrisation scheme to study behaviour at air–water interfaces

Abstract

In this article, we present a general parametrisation scheme for many-body dissipative particle dynamics (MDPD). The scheme is based on matching model components to experimental surface tensions and chemical potentials. This allows us to obtain the correct surface and mixing behaviours of complex, multicomponent systems. The methodology is tested by modelling the behaviour of nonionic polyoxyethylene alkyl ether surfactants at an air/water interface. In particular, the influence of the number of ethylene oxide units in the surfactant head group is investigated. We find good agreement with many experimentally obtained parameters, such as minimum surface area per molecule; and a decrease in the surface tension with increasing surfactant surface density. Moreover, we observe an orientational transition, from surfactants lying directly on the water surface at low surface coverage, to surfactants lying parallel or tilted with respect to the surface normal at high surface coverage. The parametrisation scheme is also extended to cover the zwitterionic surfactant lauryldimethylamine oxide (LDAO), where we provide good predictions for the surface tension at maximum surface coverage. Here, if we exceed this coverage, we are able to demonstrate the spontaneous production of micelles from the surface surfactant layer.