Transport properties of glass-forming liquids suggest that dynamic crossover temperature is as important as the glass transition temperature

Abstract

It is becoming common practice to partition glass-forming liquids into two classes based on the dependence of the shear viscosity η on temperature T . In an Arrhenius plot, ln η vs 1/ T , a strong liquid shows linear behavior whereas a fragile liquid exhibits an upward curvature [super-Arrhenius (SA) behavior], a situation customarily described by using the Vogel–Fulcher–Tammann law. Here we analyze existing data of the transport coefficients of 84 glass-forming liquids. We show the data are consistent, on decreasing temperature, with the onset of a well-defined dynamical crossover η × , where η × has the same value, η × ≈ 10 3 Poise, for all 84 liquids. The crossover temperature, T × , located well above the calorimetric glass transition temperature T g , marks significant variations in the system thermodynamics, evidenced by the change of the SA-like T dependence above T × to Arrhenius behavior below T × . We also show that below T × the familiar Stokes–Einstein relation D / T ∼ η -1 breaks down and is replaced by a fractional form D / T ∼ η - ζ , with ζ ≈ 0.85.