Investigation of Mixed Surfactant Films at Water Surface Using Molecular Dynamics Simulations

Multicomponent Langmuir monolayers are important models of organic coatings of naturally occurring water–vapor interfaces such as the surfaces of oceans or aerosol particles. We investigated mixed monolayers comprised of palmitic acid, C₁₅H₃₁COOH (PA) and 1-bromoalkanes of different chain length (C₅, C₁₀, and C₁₆) at the air–water interface employing classical molecular dynamics simulations. Different composition ratios and lateral compression of the monolayers were considered. The structural parameters, such as density profiles, and deuterium order parameter, evaluated as functions of composition and the lateral film packing, provide microscopic information about organization and dynamics of the mixed monolayers. Simulations demonstrate that stable and well mixed monolayers are formed by the mixtures of PA and BrC₁₆H₃₃ (BrCl6), whereas the two considered shorter bromoalkanes, BrC₅H₁₁ (BrC5) and BrC₁₀H₂₁ (BrC10), do not form stable films. This is in accord with earlier experimental studies. Under high lateral pressures, in PA/BrC10 mixed systems molecules of the bromoalkane readily flip in the monolayer and subsequently leave the film, while the molecules of the longer BrC16 are expelled from the PA film but no flipping occurs. These results suggest that the film collapse under pressure is preceded by squeezing-out of bromoalkanes from the PA monolayer