Calculating the free energy of self-assembled structures by thermodynamic integration

Abstract

We discuss a method for calculating free energy differences between disordered and ordered phases of self-assembling systems utilizing computer simulations. Applying an external, ordering field, we impose a predefined structure onto the fluid in the disordered phase. The structure in the presence of the external, ordering field closely mimics the structure of the ordered phase (in the absence of an ordering field). Self-consistent field theory or density functional theory provides an accurate estimate for choosing the strength of the ordering field. Subsequently, we gradually switch off the external, ordering field and, in turn, increase the control parameter that drives the self-assembly. The free energy difference along this reversible path connecting the disordered and the ordered state is obtained via thermodynamic integration or expanded ensemble simulation techniques. Utilizing Single-Chain-in-Mean-Field simulations of a symmetric diblock copolymer melt we illustrate the method and calculate the free energy difference between the disordered phase and the lamellar structure at an intermediate incompatibility chiN=20. Evidence for the first-order character of the order-disorder transition at fixed volume is presented. The transition is located at chi(ODT)N=13.65+/-0.10 for an invariant degree of polymerization of N=14 884. The magnitude of the shift of the transition from the mean field prediction qualitatively agrees with other simulations.