Theory of specific heat in glass-forming systems

Phys Rev E Stat Nonlin Soft Matter Phys. 2008 Dec;78(6 Pt 1):061504. doi: 10.1103/PhysRevE.78.061504. Epub 2008 Dec 19.

Abstract

Experimental measurements of the specific heat in glass-forming systems are obtained from the linear response to either slow cooling (or heating) or to oscillatory perturbations with a given frequency about a constant temperature. The latter method gives rise to a complex specific heat with the constraint that the zero frequency limit of the real part should be identified with thermodynamic measurements. Such measurements reveal anomalies in the temperature dependence of the specific heat, including the so called "specific heat peak" in the vicinity of the glass transition. The aim of this paper is to provide theoretical explanations of these anomalies in general and a quantitative theory in the case of a simple model of glass formation. We first present interesting simulation results for the specific heat in a classical model of a binary mixture glass former. We show that in addition to the formerly observed specific heat peak there is a second peak at lower temperatures which was not observable in earlier simulations. Second, we present a general relation between the specific heat, a caloric quantity, and the bulk modulus of the material, a mechanical quantity, and thus offer a smooth connection between the liquid and amorphous solid states. The central result of this paper is a connection between the micromelting of clusters in the system and the appearance of specific heat peaks; we explain the appearance of two peaks by the micromelting of two types of clusters. We relate the two peaks to changes in the bulk and shear moduli. We propose that the phenomenon of glass formation is accompanied by a fast change in the bulk and the shear moduli, but these fast changes occur in different ranges of the temperature. Last, we demonstrate how to construct a theory of the frequency dependent complex specific heat, expected from heterogeneous clustering in the liquid state of glass formers. A specific example is provided in the context of our model for the dynamics of glycerol. We show that the frequency dependence is determined by the same alpha -relaxation mechanism that operates when measuring the viscosity or the dielectric relaxation spectrum. The theoretical frequency dependent specific heat agrees well with experimental measurements on glycerol. We conclude the paper by stating that there is nothing universal about the temperature dependence of the specific heat in glass formers-unfortunately, one needs to understand each case by itself.

Publication types

  • Research Support, Non-U.S. Gov't