No abstract

All-atom molecular dynamics simulations and experimental characterization have been used to examine the structure and dynamics of novel evaporation-suppressing films where the addition of a water-soluble polymer to an ethylene glycol monooctadecyl ether monolayer leads to improved water evaporation resistance. Simulations and Langmuir trough experiments demonstrate the surface activity of poly(vinyl pyrrolidone) (PVP). Subsequent MD simulations performed on the thin films supported by the PVP sublayer show that, at low surface pressures, the polymer tends to concentrate at the film/water interface. The simulated atomic concentration profiles, hydrogen bonding patterns, and mobility analyses of the water-polymer-monolayer interfaces reveal that the presence of PVP increases the atomic density near the monolayer film, improves the film stability, and reduces the mobility of interfacial waters. These observations explain the molecular basis of the improved efficacy of these monolayer/polymer systems for evaporation protection of water and can be used to guide future development of organic thin films for other applications.

This study compares the performance of the all-atom molecular dynamics force fields OPLS-AA and COMPASS, and the united-atom GROMOS96 ff53a6 force field, for organic monolayers at aqueous interfaces, as a function of surface density, temperature, and system size. Where possible, comparison with experimental data was undertaken and used to scrutinize the performance of each force field. We find close agreement between the all-atom force fields (OPLS and COMPASS) and experiment for the description of organic monolayers on water. However, the united-atom force field 53a6 tends to exhibit poorer agreement than the all-atom force fields.

Mixed monolayers of 1-octadecanol (C18OH) and ethylene glycol monooctadecyl ether (C18E1) were studied to assess their evaporation suppressing performance. An unexpected increase in performance and stability was found around the 0.5:0.5 bicomponent mixture and has been ascribed to a synergistic effect of the monolayers. Molecular dynamics simulations have attributed this to an additional hydrogen bonding interaction between the monolayer and water, due to the exposed ether oxygen of C18E1 in the mixed system compared to the same ether oxygen in the pure C18E1 system. This interaction is maximized around the 0.5:0.5 ratio due to the particular interfacial geometry associated with this mixture.