The kinetic fragility of liquids as manifestation of the elastic softening

We show that the fragility $m$, the steepness of the viscosity and relaxation time close to the vitrification, increases with the degree of elastic softening, i.e. the decrease of the elastic modulus with increasing temperature, in universal way. This provides a novel connection between the thermodynamics, via the modulus, and the kinetics. The finding is evidenced by numerical simulations and comparison with the experimental data of glassformers with widely different fragilities ($33 \le m \le 115$), leading to a fragility-independent elastic master curve extending over eighteen decades in viscosity and relaxation time. The master curve is accounted for by a cavity model pointing out the roles of both the available free volume and the cage softness. A major implication of our findings is that ultraslow relaxations, hardly characterised experimentally, become predictable by linear elasticity. As an example, the viscosity of supercooled silica is derived over about fifteen decades with no adjustable parameters.Comment: 7 pages, 6 figures; Added new results, improved the theoretical sectio

Unified Theory of Activated Relaxation in Liquids over 14 Decades in Time

We formulate a predictive theory at the level of forces of activated relaxation in hard-sphere fluids and thermal liquids that covers in a unified manner the apparent Arrhenius, crossover, and deeply supercooled regimes. The alpha relaxation event involves coupled cage-scale hopping and a long-range collective elastic distortion of the surrounding liquid, which results in two inter-related, but distinct, barriers. The strongly temperature and density dependent collective barrier is associated with a growing length scale, the shear modulus, and density fluctuations. Thermal liquids are mapped to an effective hard-sphere fluid based on matching long wavelength density fluctuation amplitudes, resulting in a zeroth-order quasi-universal description. The theory is devoid of fit parameters, has no divergences at finite temperature nor below jamming, and captures the key features of the alpha time of molecular liquids from picoseconds to hundreds of seconds