Relaxation Phenomena and Thermodynamics of Liquids at Very High Pressures

Abstract

ABSTRACTComplex liquid glass-forming systems ranging from those composed of simple molecules to polymer melts and amorphous polymers have been studied extensively as a function of temperature resulting in a basic understanding of liquid-state dynamics and glass transition phenomenology as these systems are supercooled to the vitreous state. An important aspect of this problem that remains largely unexplored, and that is relevant to the topic of this symposium, involves liquid-state dynamics and vitrification (as well as crystallization) in the regime of high pressure and high density. We describe work on “fragile” to “intermediate strength” simple organic glass-forming liquids where both temperature (T) and pressure (P) are varied. Diamond anvil cells are used to achieve pressures exceeding 10 GPa. Several optical and light scattering techniques are used to explore both static and dynamic properties of these systems. High-pressure Brillouin scattering enables us to model the longitudinal relaxation time in these systems as well as their equations of state. These can now be refined by direct measurements of the pressure dependence of the glass transition, Tg(P). Finally, we summarize depolarized light scattering studies which allow us to compare both the isobaric and isothermal evolution of structural (α) and fast (β) relaxation processes.