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• W2000882014 abstract "Mass transport across surfactant-covered oil-water interfaces of microemulsions plays an important role in numerous applications. In the current work, we use coarse-grained molecular dynamics simulations to investigate model systems containing flat hexadecane-water interfaces covered by monolayers of nonionic surfactants of various lengths. Several properties of the surfactant monolayers relevant to the mass transport are considered, including the monolayer microstructure, dynamics, and a free energy barrier to the solute transport. It is observed that the dominant contribution of a surfactant monolayer to the free energy barrier is a steric repulsion caused by a local density increase inside the monolayer. The local densities, and hence the free energy barriers, are larger for monolayers composed of longer surfactants. Since it is likely that the solute transport mechanism involves a sequence of jumps between short-lived pores within a monolayer, we perform a detailed analysis of structure, size, and lifetime of these pores. We demonstrate that the pore statistics is consistent with predictions of percolation theory and apply this theory to identify the characteristic length scale of the monolayer microstructure. The obtained pore structures are sensitive to minute changes of surfactant configurations occurring on the picosecond time scale. To reduce this sensitivity, the pores are averaged over short time intervals. The optimal duration of these time intervals is estimated from analysis of dynamics of pores with diameters comparable to or exceeding the characteristic percolation length scale. The developed approach allows one to filter out transient events of the pore dynamics and to focus on events leading to substantial changes of the monolayer microstructure." @default.
• W2000882014 created "2016-06-24" @default.
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• W2000882014 date "2008-06-20" @default.
• W2000882014 modified "2023-09-24" @default.
• W2000882014 title "Molecular modeling of surfactant covered oil-water interfaces: Dynamics, microstructure, and barrier for mass transport" @default.
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• W2000882014 doi "https://doi.org/10.1063/1.2939123" @default.
• W2000882014 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/18570521" @default.
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