Polymer Glass-Formation in Variable Dimension

Abstract

We explore the nature of glass-formation in variable spatial dimensionality ($d$) based on the generalized entropy theory, a synthesis of the Adam-Gibbs model with direct computation of the configurational entropy of polymer fluids using an established statistical mechanical model. We find that structural relaxation in the fluid state asymptotically becomes Arrhenius in the $d\to \infty$ limit and that the fluid transforms upon sufficient cooling above a critical dimension near $d=8$ into a dense amorphous state with a finite positive residual configurational entropy. Direct computations of the isothermal compressibility and thermal expansion coefficient, taken to be physical measures of packing frustration, demonstrate that these fluid properties strongly correlate with the fragility of glass-formation.

A significantly extended version of the paper has appeared in Advances in Chemical Physics

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• Equation of State and Entropy Theory Approach to Thermodynamic Scaling in Polymeric Glass-Forming Liquids
• Generalized entropy theory of glass-formation in fully flexible polymer melts
• Thermodynamic-Dynamic Interrelations in Glass-Forming Polymer Fluids