Orientational bonding model for temperature dependent micellization and solubility of diblock surfactants

A lattice model for diblock surfactants that incorporates orientational bonding has been developed for studying self-assembly in dilute solutions. Using grand canonical Monte Carlo simulations with histogram reweighting and mixed field finite size scaling, we examine the effect of amphiphile architecture on phase transitions and distinguish between first order transitions that create a disordered liquid phase and higher order transitions that indicate the formation of finite sized aggregates. As the solution temperature increases, we find that the critical micelle concentration for the orientational bonding model surfactants reaches a minimum value at a temperature that can be controlled by varying the number of bonding orientations between the solvophobic surfactant monomers and the implicit solvent. This trend is qualitatively similar to experimental data for ionic and nonionic surfactants in aqueous solutions. A comparable dependence on temperature is observed in the limit of amphiphile solubility for phase separating systems. None of the model surfactants considered here undergo both a first and a higher order transition over the range of densities and temperatures examined.