Cooperativity and the freezing of molecular motion at the glass transition.

The slowing down of molecular dynamics when approaching the glass transition generally proceeds much stronger than expected for thermally activated motions. This strange phenomenon can be formally ascribed to a temperature-dependent activation energy E(T). In the present work, via measurements of the third-order nonlinear dielectric susceptibility, we deduce the increase of the number of correlated molecules N(corr) when approaching the glass transition and find a surprisingly simple correlation of E(T) and N(corr)(T). This provides strong evidence that the noncanonical temperature development of glassy dynamics is caused by a temperature-dependent energy barrier arising from the cooperative motion of ever larger numbers of molecules at low temperatures.