Universal Negative Energetic Elasticity in Polymer Chains: Crossovers among Random, Self-Avoiding, and Neighbor-Avoiding Walks

Abstract

Negative energetic elasticity in gels challenges the conventional understanding of gel elasticity; despite extensive research, a concise explanation remains elusive. In this study, we use the weakly self-avoiding walk (the Domb-Joyce model; DJ model) and interacting self-avoiding walk (ISAW) to investigate the emergence of negative energetic elasticity in polymer chains. Using exact enumeration, we show that both the DJ model and ISAW exhibit negative energetic elasticity, which is caused by effective soft-repulsive interactions between polymer segments. Moreover, we find that a universal scaling law for the internal energy of both models, with a common exponent of $7/4$, holds consistently across both random-walk-self-avoiding-walk and self-avoiding-walk-neighbor-avoiding-walk crossovers. These findings suggest that negative energetic elasticity is a fundamental and universal property of polymer networks and chains.

Identical to the journal version except for formatting and style, 13 pages, 6 figures (+ Supplemental Material: 22 pages)

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