Glassy dynamics in a liquid of anisotropic molecules: Bifurcation of relaxation spectrum

In experimental and theoretical studies of glass transition phenomena, one often finds a sharp crossover in dynamical properties at a temperature Tcr. A bifurcation of a relaxation spectrum is also observed at a temperature TB≈Tcr; both lie significantly above the glass transition temperature. In order to better understand these phenomena, we introduce a new model of glass-forming liquids, a binary mixture of prolate and oblate ellipsoids. This model system exhibits sharp thermodynamic and dynamic anomalies, such as the specific heat jump during heating and a sharp variation in the thermal expansion coefficient around a temperature identified as the glass transition temperature, Tg. The same temperature is obtained from the fit of the calculated relaxation times to the Vogel-Fulcher-Tammann (VFT) form. As the temperature is lowered, the calculated single peak rotational relaxation spectrum splits into two peaks at TB above the estimated Tg. Similar bifurcation is also observed in the distribution of short-to-intermediate time translational diffusion. Interrogation of the two peaks reveals a lower extent of dynamic heterogeneity in the population of the faster mode. We observe an unexpected appearance of a sharp peak in the product of rotational relaxation time τ2 and diffusion constant D at a temperature Tcr, close to TB, but above the glass transition temperature. Additionally, we coarse-grain the system into cubic boxes, each containing, on average, ∼62 particles, to study the average dynamical properties. Clear evidence of large-scale sudden changes in the diffusion coefficient and rotational correlation time signals first-order transitions between low and high-mobility domains.