Dielectric relaxation studies for model glass-forming liquids confined to nanoporous alumina matrices were examined together with high-pressure results. For confined liquids which show the deviation from bulk dynamics upon approaching the glass transition (the change from the Vogel-Fulcher-Tammann to the Arrhenius law), we have observed a striking agreement between the temperature dependence of the α-relaxation time in the Arrhenius-like region and the isochoric relaxation times extrapolated from the positive range of pressure to the negative pressure domain. Our finding provides strong evidence that glass-forming liquid confined to native nanopores enters the isochoric conditions once the mobility of the interfacial layer becomes frozen in. This results in the negative pressure effects on cooling. We also demonstrate that differences in the sensitivity of various glass-forming liquids to the "confinement effects" can be rationalized by considering the relative importance of thermal energy and density contributions in controlling the α-relaxation dynamics (the E(v)/E(p) ratio).

In this paper, a general equation of state (EOS) valid for fluids in the vicinity of the glass transition is derived on the basis of its isothermal precursor. This EOS is able to predict the density scaling of both isobaric and isothermal PVT data and it explicitly involves the scaling exponent γ(EOS), which is most likely straightforwardly related to the exponent of the inverse power law of some effective potential valid for viscous systems. This EOS and the density scaling are very successfully tested for representatives of several material classes (van der Waals liquids, polymer melts, ionic liquids, and even strongly hydrogen-bonded systems). Additionally, if the thermodynamic scaling of primary relaxation times can be achieved with the scaling exponent γ for a given material, then the value γ(EOS) found from fitting its PVT data to the EOS enables us to evaluate the value γ, which is always considerably smaller than γ(EOS).

When we cool down a liquid below the melting temperature, it can either crystallize or become supercooled, and then form a disordered solid called glass. Understanding what makes a liquid to crystallize readily in one case and form a stable glass in another is a fundamental problem in science and technology. Here we show that the crystallization/glass-forming tendencies of the molecular liquids might be correlated with the strength of the intermolecular attractions, as determined from the combined experimental and computer simulation studies. We use van der Waals bonded propylene carbonate and its less polar structural analog 3-methyl-cyclopentanone to show that the enhancement of the dipole-dipole forces brings about the better glass-forming ability of the sample when cooling from the melt. Our finding was rationalized by the mismatch between the optimal temperature range for the nucleation and crystal growth, as obtained for a modeled Lennard-Jones system with explicitly enhanced or weakened attractive part of the intermolecular 6–12 potential.