Local polymer dynamics under strong connectivity constraints: the dendrimer case.
The characteristics of local motion are explored by molecular dynamics simulations in a series of AB(2)-type dendrimer melts. Systems of generations 3-5 were simulated in a wide temperature range, allowing the assessment of effects associated with molecular size, proximity to the detected glasslike transitions, and the strong connectivity constraints imposed by the dendritic topology. Investigation of the mechanisms involved in local motion at short temporal and spatial scales revealed the connection between the non-Gaussian nature of monomer displacements to alpha-relaxation and the caging/decaging process under different degrees of confinement. In the latter mechanism, two characteristic localization lengths were identified: at the low temperature limit spatial localization was realized within approximately 10% of the nearest neighbor distance while at temperatures higher than the glass transition, the existence of an analogous length scale is ascribed to the geometric constraints due to the dense connectivity pattern. As the results from this study are discussed in comparison to the behavior observed in linear polymers and supercooled liquids, new insight is provided on the universal/specific mechanisms involved in local dynamics of different glass-forming systems.
Karatasos
K
K
Chemical Engineering Department, Aristotle University of Thessaloniki, Physical Chemistry Laboratory, 54124 Thessaloniki, Greece. karatas@eng.auth.gr
Lyulin
A V
AV