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J Chem Phys. 2005 Mar 15;122(11):114510.

Moderately and strongly supercooled liquids: a temperature-derivative study of the primary relaxation time scale.

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Departamento de FĂ­sica, Universidade Federal de Minas Gerais, Brazil.


The primary relaxation time scale tau(T) derived from the glass forming supercooled liquids (SCLs) is discussed within ergodic-cluster Gaussian statistics, theoretically justified near and above the glass-transformation temperature T(g). An analysis is given for the temperature-derivative data by Stickel et al. on the steepness and the curvature of tau(T). Near the mode-coupling-theory (MCT) crossover T(c), these derivatives separate by a kink and a jump, respectively, the moderately and strongly SCL states. After accounting for the kink and the jump, the steepness remains a piecewise conitnuous function, a material-independent equation for the three fundamental characteristic temperatures, T(g), T(c), and the Vogel-Fulcher-Tamman (VFT) T(0), is found. Both states are described within the heterostructured model of solidlike clusters parametrized in a self-consistent manner by a minimum set of observable parameters: the fragility index, the MCT slowing-down exponent, and the chemical excess potential of Adam and Gibbs model (AGM). Below the Arrhenius temperature, the dynamically and thermodynamically stabilized clusters emerge with a size of around of seven to nine and two to three molecules above and close to T(g) and T(c), respectively. On cooling, the main transformation of the moderately into the strongly supercooled state is due to rebuilding of the cluster structure, and is attributed to its rigidity, introduced through the cluster compressibility. It is shown that the validity of the dynamic AGM (dynamically equivalent to the standard VFT form) is limited by the strongly supercooled state (T(g) < T < T(c)) where the superrigid cooperative rearranging regions are shown to be well-chosen parametrized solidlike clusters. Extension of the basic parameter set by the observable kinetic and diffusive exponents results in prediction of a subdiffusion relaxation regime in SCLs that is distinct from that established for amorphous polymers.


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