Glassy dynamics of crystallite formation: The role of covalent bonds

Physics – Condensed Matter – Soft Condensed Matter

Scientific paper

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The manuscript has been extensively revised for clarity, 2 additional system sizes are considered to validate trends, and the

Scientific paper

We examine nonequilibrium features of collapse behavior in model polymers with competing crystallization and glass transitions using extensive molecular dynamics simulations. By comparing to "colloidal" systems with no covalent bonds but the same non-bonded interactions, we find three principal results: (i) Tangent-sphere polymers and colloids, in the equilibrium-crystallite phase, have nearly identical static properties when the temperature T is scaled by the crystallization temperature T_{cryst}; (ii) Qualitative features of nonequilibrium relaxation below T_{cryst}, measured by the evolution of local structural properties (such as the number of contacts) toward equilibrium crystallites, are the same for polymers and colloids; and (iii) Significant quantitative differences in rearrangements in polymeric and colloidal crystallites, in both far-from equilibrium and near-equilibrium systems, can be understood in terms of chain connectivity. These results have important implications for understanding slow relaxation processes in collapsed polymers, partially folded, misfolded, and intrinsically disordered proteins.

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