Density Field Thermodynamic Integration (DFTI): A "Soft" Approach to Calculate the Free Energy of Surfactant Self-Assemblies.

Abstract

Thermodynamic integration is one of the most established methods to quantify excess free energies between different metastable states. Excess intermolecular interactions in surfactant assemblies are on the scale of the energy of thermal fluctuations. Therefore, these materials can be deformed and topologically altered via relatively small mechanical stresses. It is thus intuitive to design reaction paths and associated order parameters that exploit the "soft" nature of these materials to mechanically rather than alchemically morph surfactant assemblies from state to state. Here, we propose a novel method coined "density field thermodynamic integration" (DFTI) that adopts the universality and transferability of alchemical methods while simultaneously exploiting the soft excess interactions between surfactant molecules. DFTI was designed for a rapid quantification of the free energy differences between different metastable structures in soft fluid materials. The DFTI method uses an external field coupled to the local density to mechanically morph the system between metastable states of interest. Here, we explored the capability of the DFTI method to swiftly and accurately calculate free energy differences between states. To this aim, we studied two different coarse-grained lipidic surfactant systems: (i) a fusion stalk and (ii) a worm-like micelle. Our results illustrate that DFTI can provide an efficient, versatile, and rather reliable method to calculate the free energy differences between surfactant assemblies.