Simulation of polyethylene above and below the melting point

Abstract

Polyethylene at equilibrium is studied by computer simulation. Configuration space is sampled efficiently by a novel Monte Carlo simulation scheme developed for the study of long molecules at high densities. Simulations are carried out in an isobaric-isothermal statistical-mechanical ensemble which permits calculation of the density of the polymer matrix at specified conditions of pressure and temperature. A systematic study of the polymer at different temperatures indicates a phase transition; in agreement with experiment, at low temperatures, the polyethylene model studied here crystallizes spontaneously. At temperatures above the melting point, the simulated melt is described accurately by the model.