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Thermodynamic interpretation of the scaling of the dynamics of supercooled liquids.

Casalini R, Mohanty U, Roland CM

Naval Research Laboratory, Chemistry Division, Washington DC 20375-5342, USA. casalini@ccs.nrl.navy.mil

The recently discovered scaling law for the relaxation times, tau(T,upsilon) = I(Tupsilon(gamma)), where T is temperature and upsilon the specific volume, is derived by a revision of the entropy model of the glass transition dynamics originally proposed by Avramov [J. Non-Cryst. Solids 262, 258 (2000)]. In this modification the entropy is calculated by an alternative route. The resulting expression for the variation of the relaxation time with T and upsilon is shown to accurately fit experimental data for several glass-forming liquids and polymers over an extended range encompassing the dynamic crossover. From this analysis, which is valid for any model in which the relaxation time is a function of the entropy, we find that the scaling exponent gamma can be identified with the Gruneisen constant.

Published 25 July 2006 in J Chem Phys, 125(1): 014505.
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