Influence of the torsional potential on the glass transition temperature and the structure of amorphous polyethylene

The effect of the torsional potential on several thermodynamic and structural properties of a system of polyethylene chains has been analyzed. To this end, molecular dynamics simulations of a coarse-grained model, whose sites interact through a force field with bending, torsional, and nonbonded terms, have been considered. The torsional potential has three stable configurations: gauche-, trans, and gauche+. It has been modeled using a simple functional form with only two parameters: the trans-gauche and the gauche-gauche energy barriers. In order to analyze the influence of these parameters on the properties considered in this work, five models with different values of the torsional barriers have been considered. We have observed that the glass transition temperature, the intrachain radial distribution function, the radius of gyration, and the end to end distribution functions are very sensitive to the changes in the trans-gauche torsional barrier. Moreover, at low temperatures, the interchain radial distribution function, the orientational correlation function, and the volume distribution functions of the Voronoi polyhedra, that surround every site of the polymeric chains, also depend on the trans-gauche torsional barrier. On the contrary, the gauche-gauche energy barrier has a minor influence in the properties considered in this work.