Entropy-driven crystallization in dense systems of athermal chain molecules.
We describe the direct observation of entropy-driven crystallization in simulations of dense packings of linear hard-sphere chains. Crystal nuclei form spontaneously in the phase coexistence region independently of chain length. Incipient nuclei consistently develop well defined, stack-faulted layered morphologies with a single stacking direction. These morphologies deviate markedly from those of monomeric analogs. The ordering transition is driven by the increase in translational entropy: ordered sites exhibit enhanced mobility as their local free volume becomes more spherical and symmetric.
Karayiannis
Nikos Ch
NCh
Institute for Optoelectronics and Microsystems (ISOM) and ETSII, Universidad Politécnica de Madrid (UPM), 28006 Madrid, Spain.
Foteinopoulou
Katerina
K
Laso
Manuel
M
D016880:Anisotropy; D003460:Crystallization; D019277:Entropy; D046911:Macromolecular Substances / Q000737:chemistry*; D008956:Models, Chemical
D046911:Macromolecular Substances