Boiling Temperature As a Scaling Parameter for the Microscopic Relaxation Dynamics in Molecular Liquids

Abstract

At sufficiently high temperatures, the center-of-mass microscopic diffusion dynamics of liquids is characterized by a single component, often with weak temperature dependence. In this regime, the effective cage made by the neighbor particles cannot be sustained and readily breaks down, enabling long-range diffusion. As the temperature is decreased, the cage relaxation becomes impeded, leading to a higher viscosity with more pronounced temperature dependence. On the microscopic scale, the sustained caging effect leads to a separation between a faster in-cage relaxation component and a slower cage-breaking relaxation component. The evidence for the separate dynamic components, as opposed to a single stretched component, is provided by quasielastic neutron scattering experiments. We use a simple method to evaluate the extent of the dynamic components separation as a function of temperature in a group of related aromatic molecular liquids. We find that, regardless of the glass-forming capabilities or lack thereof, progressively more pronounced separation between the in-cage and cage-breaking dynamic components develops on cooling down as the ratio of T(b)/T, where T(b) is the boiling temperature, increases. This reflects the microscopic mechanism behind the empirical rule for the glass forming capability based on the ratio of boiling and melting temperatures, T(b)/T(m). When a liquid's T(b)/T(m) happens to be high, the liquid can readily be supercooled below its T(m) because the liquid's microscopic relaxation dynamics is already impeded at T(m), as evidenced by a sustained caging effect manifested through the separation of the in-cage and cage-breaking dynamic components. Our findings suggest certain universality in the temperature dependence of the microscopic diffusion dynamics in molecular liquids, regardless of their glass-forming capabilities. Unless the insufficiently low (with respect to T(b)) melting temperature, T(m), intervenes and makes crystallization thermodynamically favorable when cage-breaking is still unimpeded and the structural relaxation is fast, the liquid is likely to become supercooled. The propensity to supercooling and eventually forming a glass is thus determined by a purely thermodynamic factor, T(b)/T(m).