The simplest model of polymer crystal exhibiting polymorphism

TL;DR

This paper introduces a minimalistic polymer model using zigzag chains and Lennard-Jones interactions to predict and analyze polymorphic structures, revealing stable lattice types and their energy hierarchy similar to real polyethylene.

Contribution

It presents the simplest model of polymer crystals that predicts multiple polymorphic lattices and their stability, aligning with experimental observations.

Findings

Identified five possible equilibrium lattices in the simplified polymer model.

Demonstrated that certain lattices are stable depending on model parameters.

Found the energy hierarchy of lattices matches that of real polyethylene.

Abstract

Almost all the polymer crystals have several polymorphic modifications. Their structure and existence conditions, as well as transitions between them are not understood even in the case of the 'model' polymer polyethylene (PE). For analysis of polymorphism in polymer crystals, we consider the simplest possible model of polymer chain: an extended flat zigzag made of 'united' atoms (replacing CH2-groups in PE chain); the united atoms belonging to different zigzags interact via Lennard-Jones potential. Analysis of potential of interaction between such zigzags allowed to predict the structure of five possible equilibrium lattices in polymer crystal built out of such zigzags. Molecular dynamics simulation of the crystal built out of flexible zigzags showed that, depending on model parameters (dimensions of the zigzag and equilibrium distance of Lennard-Jones potential), one to three of these lattices are stable in bulk at low temperatures. We have determined the model parameters at which the existing stable lattices are analogous to the ones observed in real PE and linear alkanes. The triclinic lattice has the lowest potential energy, then follows the monoclinic lattice, and the orthorhombic lattice has the highest energy, exactly as in full atomic (with hydrogens) molecular dynamics models.