Study on structure formation of short polyethylene chains via dynamic Monte Carlo simulation

Abstract

Monte Carlo (MC) simulations of structure formation for short polyethylene chains at low temperature are performed based on a recent developed method that uses coarse-grained chains on a high coordination lattice. Local short-range interactions based on rotational isomeric state (RIS) model and long-range interactions obtained from Lennard–Jones (LJ) potential are introduced during the simulation. Properties evaluated from the simulations are the mean square dimensions, anisotropy of the radius of gyration tensor, local conformation determined by the occupancy of trans state and orientation correlation functions, energy of the system, and chain packing reflected by the pair correlation functions and structure factors. All of these parameters reveal an ordering process that produces an approximation to a hexagonal crystal phase. The hexagonal structure is imposed by the presence of a diamond lattice underlying the high coordination lattice on which the simulation is performed. Folding of the chains in the crystal is mandatory, because they have fully extended lengths in excess of the dimension of the simulated periodic box. Nevertheless, the simulations demonstrate that a high degree of crystallinity can be achieved in reasonable computer time. The simulation technique should be applicable to other choices of periodic boundary conditions that do not affect the results as strongly as in the present case.