Revealing the rich dynamics of glass-forming systems by modification of composition and change of thermodynamic conditions

Secondary relaxations have been classified into two types, depending on whether they are related to the structural alpha-relaxation in properties or not. Those secondary relaxations that are related to the a-relaxation may have fundamental importance, and are called the Johari–Goldstein (JG) ß-relaxations. Two polar molecular glass-formers, one flexible and another rigid, dissolved in apolar host with higher glass transition temperature are studied by broadband dielectric spectroscopy at ambient and elevated pressure. The neat flexible glassformer diethylphthalate (DEP) has a resolved secondary relaxation which, unlike the a-relaxation, is insensitive to pressure and hence is not the JG ß-relaxation. In the solution, the JG ß-relaxation of DEP shows up in experiment and its relaxation time tß is pressure and temperature dependent like ta. The result supports the universal presence of the JG ß-relaxation in all glass-formers, and the separation between ta and tß is determined by intermolecular interaction. The rigid glass-former is cyano-benzene (CNBz) and its secondary relaxation involves the entire molecule is necessarily the JG ß-relaxation. The dielectric relaxation spectra obtained at a number of combinations of pressure and temperature at constant ta show not only unchanged is the frequency dispersion of the a-relaxation but also tß. The remarkable results indicate that the JG ß-relaxation bears a strong connection to the alpha-relaxation, and the two relaxations are inseparablewhen considering the dynamics of glass-forming systems. Experimentally, tau_alpha has been found to be a function of the product variables, T/rho^gamma, where rho is the density and gamma is a material constant. From the invariance of the ratio, tau_alphaa/tau_ß, to change of thermodynamic conditions seen in our experiment as well in other systems, it follows that tß is also a function of T/rho^gamma, with the same gamma at least approximately. Since the JG ß-relaxation is the precursor of the a-relaxation, causality implies that the T/rho^gamma-dependence originates from the JG ß-relaxation and is passed on to the alpha-relaxation