title: 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.
authors.affiliation: Faculty of Physics, University of Vienna, Sensengasse 8, 1090 Vienna, Austria.
authors.forename: Christian
authors.initials: C
authors.lastname: Leitold
authors.affiliation: Faculty of Physics, University of Vienna, Sensengasse 8, 1090 Vienna, Austria.
authors.forename: Christoph
authors.initials: C
authors.lastname: Dellago
mesh_terms: D003460:Crystallization; D016013:Likelihood Functions; D008958:Models, Molecular; D044367:Phase Transition; D011108:Polymers / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D011108:Polymers