Publications Details

Density Functional Theory of Simple Polymers in a Slit Pore: 2. The Role of Compressibility and Field Type

Curro, John G.; Weinhold, Jeffrey D.

Simple tangent, hard site chains near a hard wall are modeled with a Density Functional (DF) theory that uses the direct correlation function, c(r), as its ''input''. Two aspects of this DF theory are focused upon: (1) the consequences of variations in c(r)'s detailed form; and (2) the correct way to introduce c(r) into the DF formalism. The most important aspect of c(r) is found to be its integrated value, {cflx c}(0). Indeed, it appears that, for fixed {cflx c}(0), all reasonable guesses of the detailed shape of c(r) result in surprisingly similar density distributions, {rho}(r). Of course, the more accurate the c(r), the better the {rho}(r). As long as the length scale introduced by c(r) is roughly the hard site diameter and as long as the solution remains liquid-like, the {rho}(r) is found to be in good agreement with simulation results. The c(r) is used in DF theory to calculate the medium-induced-potential, U{sub M}(r) from the density distribution, {rho}(r). The form of U{sub M}(r) can be chosen to be one of a number of different forms. It is found that the forms for U{sub M}(r), which yield the most accurate results for the wall problem, are also those which were suggested as accurate in previous, related studies.