Numerical implementation of pseudo-spectral method in self-consistent mean field theory for discrete polymer chains

摘要

In the standard self-consistent field theory (SCFT), a polymer chain is modeled as an infinitely flexible Gaussian chain, and the partition function is calculated by solving a differential equation in the form of a modified diffusion equation. The Gaussian chain assumption makes the standard SCFT inappropriate for modeling of short polymers, and the discrete chain SCFT in which the partition function is obtained through recursive integrals has recently been suggested as an alternative method. However, the shape of the partition function integral makes this method much slower than the standard SCFT when calculated in the real space. In this paper, we implement the pseudospectral method for the discrete chain SCFT adopting the bead-spring or freely jointed chain (FJC) model, and a few issues such as the accurate discretization of the FJC bond function are settled in this process. With the adoption of the pseudospectral method, our calculation becomes as fast as that of the standard SCFT. The integral equation introduces a new boundary condition, the neutral boundary, which is not available in the standard SCFT solving the differential equation. This interesting physical situation is combined with the finite-range interaction model for the study of symmetric block copolymers within thin films. We find that the surface-perpendicular block copolymer lamellar phase becomes preferable to the surface-parallel one when both the top and bottom surfaces are neutral. Published under license by AIP Publishing.