A model for the simulation of the CnEm nonionic surfactant family derived from recent experimental results

Abstract

Using a comprehensive set of recently published experimental results for training and validation, we have developed computational models appropriate for simulations of aqueous solutions of poly(ethylene oxide) alkyl ethers, an important class of micelle- forming nonionic surfactants, usually denoted CnEm. These models are suitable for use in simulations that employ a moderate amount of coarse graining, and especially for dissipative particle dynamics (DPD), which we adopt in this work. The experimental data used for training and validation was reported earlier and pro- duced in our laboratory using dynamic light scattering (DLS) measurements performed on twelve members of the CnEm compound family yielding micelle size distribution functions and mass weighted mean aggregation numbers at each of several surfactant concentrations. The range of compounds and quality of the experimental results were designed to support the development of computational models. An essential feature of this work is that all simulation results were analyzed in a way that is consistent with the experimental data in that proper account is taken of the fact that a broad distribution of micelle sizes exists and so mass weighted averages (rather than number weighted averages) over this distribution are required for the proper comparison of simulation and experimental results. The resulting DPD force field reproduces several important trends seen in the experimental critical micelle concentrations and and mass averaged mean aggregation numbers with respect to surfactant characteristics and concentration. We feel it can be used to investigate a number of open questions regarding micelle sizes and shapes and their dependence on surfactant concentration for this important class of nonionic surfactant.