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Dynamic mean-field models from a nonequilibrium thermodynamics perspective.

Markus Hütter1, Iliya V Karlin, Hans Christian Ottinger

  • 1Department of Materials, Institute of Polymers, ETH-Zürich, CH-8092 Zürich, Switzerland. mhuetter@mit.edu

Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics
|August 26, 2003
PubMed
Summary

This study uses nonequilibrium thermodynamics to evaluate mean-field models. We show one model is thermodynamically valid, while a Gaussian approximation for polymer solutions is shown to be defective.

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Area of Science:

  • Non-equilibrium thermodynamics
  • Polymer physics
  • Statistical mechanics

Background:

  • Complex dynamic models often rely on mean-field approximations.
  • Evaluating the thermodynamic consistency of these approximations is crucial.

Purpose of the Study:

  • To examine mean-field models using nonequilibrium thermodynamics.
  • To assess the thermodynamic admissibility of specific approximations in polymer dynamics.

Main Methods:

  • Utilized the double-generator general equation for nonequilibrium reversible-irreversible coupling (GENERIC) framework.
  • Applied the framework to two distinct model systems.

Main Results:

  • The de Gennes model for the coil-stretch transition in polymers was found to be thermodynamically admissible.

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  • A Gaussian approximation for hydrodynamic interactions in polymer solutions was identified as thermodynamically defective.

    • Conclusions:

    • The GENERIC framework provides a rigorous method for validating thermodynamic models.
    • Certain common approximations, like the Gaussian approximation, may violate fundamental thermodynamic principles.