Numerical algorithms for solving self-consistent field theory reversely for block copolymer systems.

Abstract

Besides dictating the equilibrium phase diagram, the rugged free-energy landscape of AB block copolymers gives rise to a multitude of non-equilibrium phenomena. Self-consistent field theory (SCFT) can be employed to calculate the mean-field free energy, , of a non-equilibrium unstable state that is characterized by a given spatial density distribution, , in the incompressible system. Such a free-energy functional is the basis of describing the structure formation by dynamic SCFT techniques or the identification of minimum free-energy paths via the string method. The crucial step consists in computing the external potential fields that generate the given density distribution in the corresponding system of non-interacting copolymers, i.e., the potential-to-density relation employed in equilibrium SCFT calculations has to be inverted (reverse SCFT calculation). We describe, generalize, and evaluate the computational efficiency of two different numerical algorithms for this reverse SCFT calculation-the Debye-function algorithm based on the structure factor and the field-theoretic umbrella-potential (FUP) algorithm. In contrast to the Debye-function algorithm, the FUP algorithm only yields the exact mean-field values of the given target densities in the limit of a strong umbrella potential, and we devise a two-step variant of the FUP algorithm that significantly mitigates this issue. For Gaussian copolymers, the Debye-function algorithm is more efficient for highly unstable states that are far away from the equilibrium, whereas the improved FUP algorithm outperforms the Debye-function algorithm closer to metastable states and is easily transferred to more complex molecular architectures.