Secondary dynamics in glass formers: Relation with the structural dynamics and the glass transition

In this paper, we study secondary relaxations in a neat glass former close and below the glass transition. The pressure and temperature dependences of the characteristic relaxation frequencies were investigated to find a connection between structural and secondary relaxations and the microscopic mechanism at the basis of the latter. We found that the ratio between the relaxation time of the structural and secondary processes is almost constant when considered at different values of temperature and pressure corresponding to the glass transition (same value of structural relaxation time). This result is also related to the finding of a constant broadness of the structural peak. We propose to use such dynamic relation between the two processes to distinguish between intramolecular secondary relaxation, reflecting the local motion of molecular subgroups, and intermolecular secondary relaxation, called also Johari–Goldstein process, originating by a local motion of the whole molecule.