English

Folding mechanism of a polymer chain with short-range attractions

Soft Condensed Matter 2016-08-17 v1 Statistical Mechanics Computational Physics

Abstract

We investigate the crystallization of a single, flexible homopolymer chain using transition path sampling (TPS). The chain consists of N identical spherical monomers evolved according to Langevin dynamics. While neighboring monomers are coupled via harmonic springs, the non-neighboring monomers interact via a hard core and a short-ranged attractive potential. For a sufficiently small interaction range {\lambda}, the system undergoes a first-order freezing transition from an expanded, disordered phase to a compact crystalline state. Using a new shooting move tailored to polymers combined with a committor analysis, we study the transition state ensemble of an N=128 chain and search for possible reaction coordinates based on likelihood maximization. We find that typical transition states consist of a crystalline nucleus with one or more chain fragments attached to it. Furthermore, we show that the number of particles in the crystalline core is not well suited as a reaction coordinate. We then present an improved reaction coordinate, which includes information from the potential energy and the overall crystallinity of the polymer.

Keywords

Cite

@article{arxiv.1502.07172,
  title  = {Folding mechanism of a polymer chain with short-range attractions},
  author = {Christian Leitold and Christoph Dellago},
  journal= {arXiv preprint arXiv:1502.07172},
  year   = {2016}
}