Correlations between isobaric and isochoric fragilities and thermodynamical scaling exponent for glass-forming liquids

Abstract

Two correlations concerning the isobaric and isochoric fragilities, m(P) and m(V), as well as the scaling exponent gamma reported by Casalini and Roland [Phys. Rev. E 72, 031503 (2005)] have been examined for several van der Waals and hydrogen-bonded glass formers. It has been pointed out that the correlations lead to some serious inconsistency with the exponent gamma, which is expected to be a constant dependent only on material, but varies also on pressure if experimentally found pressure dependences of m(P) are taken into account. This problem could be solved in the case of van der Waals liquids, but then at least one of the correlations becomes dependent on thermodynamic conditions, and consequently, loses its universality. However, some H-bonded systems, due to properties of hydrogen bonding, have been well argued not to be included to determine the correlations independently of thermodynamic conditions. Furthermore, it has been noticed that another correlation concerning the fragility, between m(P) and the structural relaxation peak breadth, yields discrepancies in comparison with results of experiments under elevated pressure.