title: Density-functional theory and Monte Carlo simulation for the surface structure and correlation functions of freely jointed Lennard-Jones polymeric fluids.
abstract: We present a nonlocal density-functional theory of polymeric fluids consisting of freely jointed Lennard-Jones chains with explicit consideration of the segment size, van der Waals attraction, and structural correlations due to chain connectivity. The excess Helmholtz energy functional is derived from a modified fundamental measure theory for the short-ranged repulsion and the first-order thermodynamic perturbation theory for chain connectivity. The contribution of the long-ranged attraction to the Helmholtz energy functional is taken into account using a quadratic density expansion with the direct correlation function obtained from the first-order mean-spherical approximation. The numerical performance of the density-functional theory is compared well with the simulation results from this work as well as those from the literature for the segment-level density profiles and correlation functions of Lennard-Jones chains in slit pores, near isolated nanoparticles, or in bulk.
authors.affiliation: Department of Chemical and Environmental Engineering, University of California, Riverside, 92521-0425, USA.
authors.forename: Zhidong
authors.initials: Z
authors.lastname: Li
authors.forename: Dapeng
authors.initials: D
authors.lastname: Cao
authors.forename: Jianzhong
authors.initials: J
authors.lastname: Wu