Coarse-grained polyethylene: 1. The simplest model for the orthorhombic crystal

Abstract

The coarse-grained model of polyethylene and alkanes (the united-atom model, in which each CH2 group is represented by a single bead) was proposed several decades ago. It is widely applied in molecular dynamics simulations. For different tasks, the models with different geometrical and force parameters are used. Until now, it was thought that the coarse-grained model of polyethylene cannot reproduce the orthorhombic crystalline phase, which is typical of this polymer. In the present study, we analyze the simplest coarse-grained model of polyethylene. In this model, the Lennard-Jones potential (6–12) is adopted for van der Waals interactions between the beads of different chains. Of the bonded interactions, only the “valence” bonds between beads and the “bond” and “torsion” angles are taken into account, whereas the cross terms between them are disregarded. We consider the model variation in which the bead (the force center with the mass of a CH2 group) is displaced from the center of the carbon atom and all the interactions, both bonded and nonbonded, are defined by the positions of these beads. For this model, we find the area of geometrical parameters (the displacement value and the van der Waals radius of the bead) in which all the three known crystalline phases of polyethylene are at equilibrium at low temperatures. We choose the force field constants for the model so that its oscillation spectrum reproduces the low-frequency part of the inelastic neutron scattering spectrum of the orthorhombic polyethylene. It proved to be that this choice can be made unambiguously. We compare the dispersion curves in the terahertz range with experimental data on the Raman scattering and infrared spectroscopy, and discuss the advantages and disadvantages of the analyzed simplest coarse model.