Structure of a freely jointed tangent hard-sphere chain in hard slit pores

Abstract

A density functional theory (DFT), which is based both on the density functional expansion of the first-order direct correlational functional with respect to the bulk molecular density and on the contact-value theorem at the hard wall, has been developed for studying the structure of a freely jointed tangent hard-sphere chain in hard slit pores. Two different second-order direct correlation functions (DCFs) based on the Polymer Reference Interaction Site model (PRISM) coupled with the Percus–Yevick closure relation and the Wertheim's first-order perturbation theory modified by Yu and Wu (modified TPT1) were used as inputs. The calculated results show that (i) the PRISM theory is in excellent agreement with the computer simulations even for high densities, and that (ii) the calculated local density distribution strongly depends on the second-order DCFs as well as the DFT version employed.