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? 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? 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? 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? estimates on the experimental method used to derive the relaxation function.