Temperature of systems out of thermodynamic equilibrium

Details Temperature of systems out of thermodynamic equilibrium Temperature of systems out of thermodynamic equilibrium

2008-04-28

arxiv.org/abs/0804.4456v2

The Journal of Chemical Physics 129 (2008) 044508

Physics

Condensed Matter

Soft Condensed Matter

Scientific paper

10.1063/1.2958913

Two phenomenological approaches are currently used in the study of the vitreous state. One is based on the concept of fictive temperature introduced by Tool [Jour. Research Nat. Bur. Standards 34, 199 (1945)] and recently revisited by Nieuwenhuizen [Phys. Rev. Lett. 80, 5580 (1998)]. The other is based on the thermodynamics of irreversible processes initiated by De Donder at the beginning of the last century [L'Affinit\'e (Gauthier-Villars, Paris, 1927)] and recently used by M\"oller and co-workers for a thorough study of the glass transition [J. Chem. Phys. 125, 094505 (2006)]. This latter approach leads to the possibility of describing the glass transition by means of the freezing-in of one or more order parameters connected to the internal structural degrees of freedom involved in the vitrification process. In this paper, the equivalence of the two preceding approaches is demonstrated, not only for glasses, but in a very general way for any system undergoing an irreversible transformation. This equivalence allows the definition of an effective temperature for all systems departed from equilibrium generating a positive amount of entropy. In fact, the initial fictive temperature concept of Tool leads to the generalization of the notion of temperature for systems out of thermodynamic equilibrium, for which glasses are just particular cases.

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