Thermodynamic description of the glassy state

In the fifties, sixties and seventies of last century quite some effort was devoted to find a thermodynamic description of the glassy state. The efforts failed on the experimental test of the so-called Ehrenfest relations. The resulting Prigogine-defay ratio should be equal to unity in the considered theories, while experimental values were typically between 2 and 5.
[L27] draws attention to unexpected behavior of the dynamical transition of the so-called p-spin model. In [L30] the analysis of the so-called marginal state of the p-spin model showed that a two-temperature approach worked in the dynamical regime.
The letter [L31] explains how the old paradox of Ehrenfest relations and Prigogine-Defay ratio gets resolved in this two-temperature - two-entropy approach.
This all became more clear in [L32] and [P49], where systems having two sets of modes are considered: fast ones that are just in equilibrium with the bath (not yet taken into account there) and slow ones, so slow that they set out their own equilibrium at an effective temperature that depends slowly on time. The associated variable to the effective temperature is the configurational entropy, here in the definition of entropy of slow modes. The time-dependencies are such that previous assumptions of being near to equilibrium are not well enough satisfied, and, as a result, the Prigogine-Defay ratio can take any value, even negative.
A richer model, in which all these and other standard glassy properties are included, [I4], was worked out in great detail by my PhD student Luca Leuzzi, [P53] and [P57].
Several of these aspects became apparant in an exactly solvable model for a model glass, [L29]. A pedagogic paper on this field is [P56].
In [N1] en [N2] geef ik een beschrijving in het Nederlands Tijdschrift voor Natuurkunde.

Book

Luca Leuzzi and Theo M. Nieuwenhuizen,
Thermodynamics of the Glassy State, monograph with foreword by Giorgio Parisi.
Taylor and Francis, 2007, pp 1-344


[P60] L. Leuzzi and Th.M. N., Exactly solvable model glass with facilitated dynamics, J. Phys. Cond. Mat. 14 (2002) 1637-1649

[P57] Luca Leuzzi and Theo M. N., Inherent Structures in models for fragile and strong glass, Phys. Rev. E 64, 066125 (2001) (15 pages)

[P56] Th.M. N., Formulation of thermodynamics for the glassy state: configurational energy as a modest source of energy, J. Chem. Phys. 115 8083-8088 (2001)

[P53] Luca Leuzzi and Th. M. N., Effective temperatures in an exactly solvable model for a fragile glass, Phys. Rev. E 64, 011508 (2001) (24 pages)

[P50] A.E. Allahverdyan, Th.M. N., and D.B. Saakian, Model glasses coupled to two different heat baths, Eur. Phys. J. B 16 (2000) 317-355

[P49] Th.M. N., Thermodynamic picture of the glassy state gained from exactly solvable models, Phys. Rev. E 61 (2000) 267-292

[I4] Th.M. N., Solvable model for the standard folklore of the glassy state, cond-mat/9911052

[L32] Th.M. N., Thermodynamics of the glassy state: effective temperature as an additional system parameter, Phys. Rev. Lett. 80 (1998) 5580-5583

[L31] Th.M. N., Ehrenfest relations at the glass transition: solution to an old paradox, Phys. Rev. Lett. 79 (1997) 1317-1320

[L30] Th.M. N., Thermodynamic description of a dynamical glassy transition, J. Phys. A Lett. 31 (1998) L201-L207

[L29] Th.M. N., Solvable glassy system: static versus dynamical transition, Phys. Rev. Lett. 78 (1997) 3491-3494

[L27] Th.M. N., To maximize or not to maximize the free energy of glassy systems, Phys. Rev. Lett 74 (1995) 3463-3466