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Theory of Surface Micelles of Semifluorinated Alkanes
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Surface structures of semifluorinated alkanes F(CF2)n(CH2)mH (referred to as FnHm) spread on the air/water interfaceare investigated theoretically. The study is focused on the disklike surface micelles that were recently identified byAFM and scattering techniques at sufficiently high surface concentrations. We show that (1) the micelles emerge asa result of liquid/liquid (rather than liquid/gas) phase separation in the Langmuir layer; (2) the micelles are islandsof the higher-density phase with roughly vertical orientation of FnHm molecules (F-parts extend toward air, H-partstoward water) and the matrix is the lower density-phase where the FnHm diblocks are nearly parallel to the watersurface; (3) the micelles and the hexagonal structure they form are stabilized by the electrostatic interactions whichare mainly due to the vertical dipole moments of the CF2- CH2 bonds in the vertical phase; and (4) the electrostaticrepulsive interactions can serve to suppress the micelle size polydispersity.
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