Wednesday, October 19, 2011: 4:40 PM
101 A (Minneapolis Convention Center)
Mechanisms of molecular transport across oil-water interfaces covered by non-ionic surfactants are investigated using coarse-grained molecular dynamics simulations. Resistance of the surfactant monolayer to the solute transport is shown to be controlled by dense regions in the monolayer. The dense regions are formed on both sides of the dividing surface and the barrier to the solute transport is created by those of them experiencing unfavorable interactions with the solute. Resistance to the transport of a hydrophobic (hydrophilic) solute increases with the excess density of the head (tail) group region of the monolayer, which in turn increases with the length of the surfactant head (tail) group. Barriers for solute transport through surfactant monolayers are also influenced by the solute size. However, the extent of this influence is determined by the monolayer thickness and the solute structure and composition. For example, it is shown that resistance offered by thin monolayers to transport of linear oligomers is relatively insensitive to the solute length. The barrier sensitivity to the length of these solutes increases with the monolayer thickness. In addition to the static barriers, the solute transport is shown to be affected by dynamic barriers due to a non-adiabatic coupling of the monolayer surface with the solute position and configuration. This coupling leads to deviations of the system dynamics from the Minimal Energy Path. The deviations are most significant in the neighborhood of the static energy barrier, which effectively leads to an increase in the barrier for the solute transport.