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  • Title: A macroscopic model that connects the molar excess entropy of a supercooled liquid near its glass transition temperature to its viscosity.
    Author: Matsuoka H.
    Journal: J Chem Phys; 2012 Nov 28; 137(20):204506. PubMed ID: 23206018.
    Abstract:
    For a deeply supercooled liquid near its glass transition temperature, we suggest a possible way to connect the temperature dependence of its molar excess entropy to that of its viscosity by constructing a macroscopic model, where the deeply supercooled liquid is assumed to be a mixture of solid-like and liquid-like micro regions. In this model, we assume that the mole fraction x of the liquid-like micro regions tends to zero as the temperature T of the liquid is decreased and extrapolated to a temperature T(g)(*), which we assume to be below but close to the lowest glass transition temperature T(g) attainable with the slowest possible cooling rate for the liquid. Without referring to any specific microscopic nature of the solid-like and liquid-like micro regions, we also assume that near T(g), the molar enthalpy of the solid-like micro regions is lower than that of the liquid-like micro regions. We then show that the temperature dependence of x is directly related to that of the molar excess entropy. Close to T(g), we assume that an activated motion of the solid-like micro regions controls the viscosity and that this activated motion is a collective motion involving practically all of the solid-like micro-regions so that the molar activation free energy Δg(a) for the activated motion is proportional to the mole fraction, 1 - x, of the solid-like micro regions. The temperature dependence of the viscosity is thus connected to that of the molar excess entropy s(e) through the temperature dependence of the mole fraction x. As an example, we apply our model to a class of glass formers for which s(e) at temperatures near T(g) is well approximated by s(e) ∝ 1 - T(K)∕T with T(K) < T(g) ≅ T(g)(*) and find their viscosities to be well approximated by the Vogel-Fulcher-Tamman equation for temperatures very close to T(g). We also find that a parameter a appearing in the temperature dependence of x for a glass former in this class is a measure for its fragility. As this class includes both fragile and strong glass formers, our model applies to both fragile and strong glass formers. We estimate the values of three parameters in our model for three glass formers in this class, o-terphenyl, 3-bromopentane, and Pd(40)Ni(40)P(20), which is the least fragile among these three. Finally, we also suggest a way to test our assumption about the solid-like and liquid-like micro regions by means of molecular dynamics simulations of model liquids.
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