Journal of Chemical Physics, Vol.103, No.8, 3230-3239, 1995
Interrelation Between Density-Functional and Self-Consistent-Field Formulations for Inhomogeneous Polymer Systems
We provide a bridge between the density functional and self-consistent-field formulations for inhomogeneous polymer systems by deriving the self-consistent-field equations from a density functional approach. The density functional theory employs the zeroth-order inhomogeneous model of Gaussian chains in the presence of interacting interfaces (or more generally of chains whose single chain distribution functions are derivable from a diffusion equation). Nonideality is represented, for simplicity, using a random mixing model, and an implicit formal solution is used for the idea! free energy functional. Application of the standard density functional variational principle produces the self-consistent-held equations and provides a method for generating analytical approximations both to the density functional and to the self-consistent-field equations. The final density functional emerges in the form of a Landau-type expansion about an analytically tractable zeroth-order inhomogeneous reference system, and the important presence of chain connectivity contributions is quite evident. We illustrate the theory by analytically computing the leading contribution to the inhomogeneous density profile induced by the presence of a polymer-surface interaction in a polymer melt that is confined by an impenetrable surface. Future works will extend these analytical computations to treat surface segregation in multicomponent polymer systems with interacting impenetrable interfaces.
Keywords:NONUNIFORM POLYATOMIC SYSTEMS;BLOCK CO-POLYMERS;STATISTICAL-MECHANICS;RENORMALIZATION-GROUP;PHASE-TRANSITIONS;LIQUID INTERFACE;EXCLUDED VOLUME;BLENDS;TENSION;MODEL