Chemical potential and equations of state of hard core chain molecules

Abstract

A novel approach is presented for the development of equations of state for chain molecules. The basic assumptions of the approach are supported by results of computer simulations of the chemical potential of athermal chains. Our model establishes a bridge between some elements of Wertheim's thermodynamic perturbation theory and the generalized Flory theory. New equations of state are presented for freely jointed tangent hard-sphere chains which are shown to be more accurate than other existing equations. Extensions of our approach are also presented for branched polymers and blends of polymers.

Polymer density functional theory approach based on scaling second-order direct correlation function

“…(39) in Ref. [14] conforms more to that in Ref. [16] for low bulk site packing fraction, while for high bulk site packing fraction, the EOS denoted by Eq.…”

Molecular Simulations of Hydrogels

“…In the 1990s Escobedo and de Pablo published a series of simulation studies of hydrogels [53][54][55] accompanied by methodological developments to enable MC simulations of hard particle networks at constant pressure and fixed chemical potential of the solvent [56][57][58][59][60]. A thermal polymer was modeled by a square-well potential.…”

An effective-colloid pair potential for Lennard-Jones colloid–polymer mixtures

“…The potential energy and the radius of gyration were computed by ensemble averaging; their statistical errors were estimated using block averages by the Flyvbjerg-Petersen method. 15 The excess chemical potential was calculated by the method of incremental Rosenbluth appending of Escobedo and de Pablo, 16 using up to four appended monomers.…”