Cooperativity at the glass transition: A perspective from facilitation on the analysis of relaxation in modulated calorimetry.

The glass transition region in nonconfined polymeric and low-molecular-weight supercooled liquids is probed by temperature-modulated calorimetry at a frequency of 3.3 mHz. From the distribution of relaxation times derived by analyzing the complex heat capacity, the number N_{α} of cooperatively rearranging units is estimated. This is done by resorting to a method in which cooperative motion is viewed as a result of a spontaneous regression of energy fluctuations. After a first, local, structural transition occurs, the energy threshold for the rearrangement of adjacent molecular units decreases progressively. This facilitation process is associated to a corresponding evolution of the density of states in a canonical representation and may be considered as a continuous spanning through different dynamic states toward a condition in which configurational constraints disappear. A good agreement is found with the N_{α} values obtained from the same calorimetric data within the framework of Donth's fluctuation theory. It is shown that, at variance from previous treatments, N_{α} can be estimated from just the relaxation function, without resorting to the knowledge of the configurational entropy. Examples point to a modest dependence of the N_{α} estimates on the experimental method used to derive the relaxation function.