The new insight into dynamic crossover in glass forming liquids from the apparent enthalpy analysis

Cesar Martinez-Garcia, Julio; Martinez-Garcia, Jorge; Rzoska, Sylwester J.; Hulliger, Jürg (2012). The new insight into dynamic crossover in glass forming liquids from the apparent enthalpy analysis. The Journal of Chemical Physics, 137(6), 064501. Melville, N.Y.: American Institute of Physics 10.1063/1.4739750

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One of the most intriguing phenomena in glass forming systems is the dynamic crossover (T(B)), occurring well above the glass temperature (T(g)). So far, it was estimated mainly from the linearized derivative analysis of the primary relaxation time τ(T) or viscosity η(T) experimental data, originally proposed by Stickel et al. [J. Chem. Phys. 104, 2043 (1996); J. Chem. Phys. 107, 1086 (1997)]. However, this formal procedure is based on the general validity of the Vogel-Fulcher-Tammann equation, which has been strongly questioned recently [T. Hecksher et al. Nature Phys. 4, 737 (2008); P. Lunkenheimer et al. Phys. Rev. E 81, 051504 (2010); J. C. Martinez-Garcia et al. J. Chem. Phys. 134, 024512 (2011)]. We present a qualitatively new way to identify the dynamic crossover based on the apparent enthalpy space (H(a)(') = dlnτ/d(1/T)) analysis via a new plot lnH(a)(') vs. 1∕T supported by the Savitzky-Golay filtering procedure for getting an insight into the noise-distorted high order derivatives. It is shown that depending on the ratio between the "virtual" fragility in the high temperature dynamic domain (m(high)) and the "real" fragility at T(g) (the low temperature dynamic domain, m = m(low)) glass formers can be splitted into two groups related to f < 1 and f > 1, (f = m(high)∕m(low)). The link of this phenomenon to the ratio between the apparent enthalpy and activation energy as well as the behavior of the configurational entropy is indicated.

Item Type:

Journal Article (Original Article)


08 Faculty of Science > Departement of Chemistry and Biochemistry

UniBE Contributor:

Hulliger, Jürg




American Institute of Physics




Factscience Import

Date Deposited:

04 Oct 2013 14:38

Last Modified:

08 Jun 2016 10:32

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Web of Science ID:




URI: (FactScience: 222594)

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