Long Wavelength Thermal Density Fluctuations in Molecular and Polymer Glass-Forming Liquids: Experimental and Theoretical Analysis under Isobaric Conditions.

We establish via an in-depth analysis of experimental data that the dimensionless compressibility (proportional to the dimensionless amplitude of long wavelength thermal density fluctuations) of one-component normal and supercooled liquids of chemically complex nonpolar and weakly polar molecules and polymers follows extremely well a surprisingly simple and general temperature dependence over an exceptionally wide range of pressures and temperatures. A theoretical basis for this behavior is shown to exist in the venerable van der Waals model and its more modern interpretations. Although associated hydrogen-bonding (and to a lesser degree strongly polar) liquids display modestly more complex behavior, rather simple temperature and pressure dependences are also discovered. A new approach to collapse the temperature- and pressure-dependent dimensionless compressibility data onto a master curve is formulated that differs from the empirical thermodynamic scaling approach. As a practical matter, we also find that the dimensionless compressibility scales well as an inverse power law with temperature with an exponent that is system dependent and decreases with pressure. At very high pressures and low temperatures, the thermal liquid behavior appears to approach (but not reach) a repulsion-dominated random close packing limit. All these findings are relevant to our recent theoretical work on the problem of activated relaxation and vitrification of supercooled molecular and polymeric liquids.