Open and Anisotropic Soft Regions in a Model Polymer Glass

The vibrational dynamics of a model polymer glass is studied by Molecular Dynamics simulations. The focus is on the “soft” monomers with high participation to the lower-frequency vibrational modes contributing to the thermodynamic anomalies of glasses. To better evidence their role, the threshold to...

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Bibliographic Details
Main Authors: Carlo Andrea Massa, Francesco Puosi, Antonio Tripodo, Dino Leporini
Format: Article
Language:English
Published: MDPI AG 2021-04-01
Series:Polymers
Subjects:
Online Access:https://www.mdpi.com/2073-4360/13/8/1336
Description
Summary:The vibrational dynamics of a model polymer glass is studied by Molecular Dynamics simulations. The focus is on the “soft” monomers with high participation to the lower-frequency vibrational modes contributing to the thermodynamic anomalies of glasses. To better evidence their role, the threshold to qualify monomers as soft is made severe, allowing for the use of systems with limited size. A marked tendency of soft monomers to form quasi-local clusters involving up to 15 monomers is evidenced. Each chain contributes to a cluster up to about three monomers and a single cluster involves a monomer belonging to about 2–3 chains. Clusters with monomers belonging to a single chain are rare. The <i>open</i> and <i>tenuous</i> character of the clusters is revealed by their fractal dimension <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mi>d</mi><mi>f</mi></msub><mo><</mo><mn>2</mn></mrow></semantics></math></inline-formula>. The inertia tensor of the soft clusters evidences their <i>strong anisotropy</i> in shape and remarkable <i>linear</i> correlation of the two largest eigenvalues. Owing to the limited size of the system, finite-size effects, as well as dependence of the results on the adopted polymer length, cannot be ruled out.
ISSN:2073-4360