Langmuir, Vol.17, No.5, 1773-1783, 2001
Molecular simulation of a dichain surfactant water carbon dioxide system. 1. Structural properties of aggregates
Molecular dynamics simulation of a dichain surfactant + water + carbon dioxide (solvent) system is performed to study the structural properties of reversed micelle-like surfactant aggregates formed in the system. The simulations use a detailed and realistic molecular model for the surfactant molecule and explicit representation of the water and solvent molecules to enable quantitative comparisons with a prior experimental (small-angle neutron scattering) study. The results of the simulation are found to be in reasonable agreement with experimental values. The simulations show that the size and shape of the surfactant aggregates depends on their water-to-surfactant ratio. A higher water-to-surfactant ratio results in larger and more spherical aggregates. The two distinct tails of the surfactant molecule exhibit different conformations in carbon dioxide indicating contrasting CO2-philic behavior. The perfluoroalkane tails assume more extended conformation than the alkane tails. The microstructure of the aqueous core reveals that the water molecules in the interfacial region are strongly oriented in response to the electric fields of the anionic headgroups and sodium counterions, while water near the center of the core approaches bulklike properties with the presence of a hydrogen-bonded network.