Folding mechanism of a polymer chain with short-range attractions
Abstract
We investigate the crystallization of a single, flexible homopolymer chain using transition path sampling. 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 λ, 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.
- Publication:
-
Journal of Chemical Physics
- Pub Date:
- October 2014
- DOI:
- 10.1063/1.4896560
- arXiv:
- arXiv:1502.07172
- Bibcode:
- 2014JChPh.141m4901L
- Keywords:
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- Condensed Matter - Soft Condensed Matter;
- Condensed Matter - Statistical Mechanics;
- Physics - Computational Physics
- E-Print:
- J. Chem. Phys. 141, 134901 (2014)