Hari O. S. Yadav, Shogo Harada, An-Tsung Kuo, Shingo Urata, and Wataru Shinoda
Mol Phys, in press, DOI:10.1080/00268976.2021.1910355.
The hemimicelle formation of long-chain semi-fluorocarbon diblocks at the air-water interface is studied using coarse-grained molecular dynamics simulations with a SPICA force field. From a series of simulations with varying the number of chains, the critical saturated size of a single micelle was predicted; its structural metrics such as the hexagonal chain packing order, density distribution, shape, mean diameter, and the orientation of the fluorinated (F-blocks) and hydrogenated segments (H-blocks) at the interface were found to be consistent with the previous experimental and atomistic simulation results. The diblock assemblies larger than the saturated size spontaneously split into multiple micelles separated by a metastable parallel phase (P-phase). This P-phase could be the reason for the non-coalescence and elastic behavior of the hemimicelle assemblies. From the simulation with a low molecular arrangement area, the mechanism of the micelle formation of saturated sizes is illustrated. The results reveal that the mutual-phobicity and interfacial tension difference of F- and H-blocks with the water are sufficient to drive the self-assembly and can provide a significant thermodynamic stability to the micelles, where the increasing packing strain between the layer curvature and the planarizing water surface tension can determine the size of the saturated hemimicelles.-