Description of the Primary Relaxation in Supercooled Liquids Through the   Timescale Steepness Function
  The primary relaxation in glass forming supercooled liquids (SCLs) above the glass transformation temperature T_g is discussed in terms of the first-order (steepness) and the second-order (curvature) temperature derivatives of the observed primary relaxation timescale. We report new insights into the problem of the domain of the Vogel-Fulcher-Tamman (VFT) equation, raised by Stickel et al. (J. Chem. Phys.,1995, 1996) and discussed by Richert and Angell (ibid., 1998). A new ergodic-cluster Gaussian statistical approach to the problem is given based on Onsager's thermodynamic principle. The primary relaxation is described by the VFT equation below the crossover temperature T_c (known from mode coupling theory (MCT)), and above T_c by an extended (VFTE) equation obtained after accounting for cluster-size fluctuations. The timescale is parametrized by a finite number of observable parameters such as the steepness function m_T, the MCT slowing-down exponent gamma_c, and the VFT and VFTE strength indices D_g and D_c. The latter are defined at T_g and T_c, respectively, for the strongly and moderately SCL states, which show absolute thermodynamic instability at the same VFT temperature T_0, associated with the Kauzmann temperature. For both states the limiting cluster-size characteristics are derived from experiment. A thermodynamic-dynamic correspondence is established between the dynamic VFT equation and the thermodynamic Adam and Gibbs model. The problem of the irregular SCLs, which are not consistent with the standard VFT equation, such as salol, ortho-terphenyl, and bis-methoxy-enyl-cyclohexane, is also discussed. 
Valery B. Kokshenev, Pablo D. Borges, and Neil S. Sullivan