Affiliation:
1. Laboratory of Polymer and Soft Matter Dynamics, Experimental Soft Matter and Thermal Physics (EST), Université libre de Bruxelles (ULB) , Brussels 1050, Belgium
Abstract
The Meyer–Neldel compensation law, observed in a wide variety of chemical reactions and other thermally activated processes, provides a proportionality between the entropic and the enthalpic components of an energy barrier. By analyzing 31 different polymer systems, we show that such an intriguing behavior is encountered also in the slow Arrhenius process, a recently discovered microscopic relaxation mode, responsible for several equilibration mechanisms both in the liquid and the glassy state. We interpret this behavior in terms of the multiexcitation entropy model, indicating that overcoming large energy barriers can require a high number of low-energy local excitations, providing a multiphonon relaxation process.
Funder
Action de Recherche Concertée ULB
Subject
Physical and Theoretical Chemistry,General Physics and Astronomy
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