Dynamical signature of two “ideal glass transitions” in nematic liquid crystals

Abstract

A temperature scaling analysis using the same mode coupling theory (MCT) scaling relationships employed for supercooled liquids is applied to optical heterodyne detected optical Kerr effect data for four liquid crystals. The data cover a range of times from ∼1 ps to 100 ns and a range of temperatures from ∼50 K above the isotropic to nematic phase transition temperature TNI down to ∼TNI. The slowest exponential component of the data obeys the Landau–de Gennes (LdG) theory for the isotropic phase of liquid crystals. However, it is also found that the liquid crystal data obey MCT scaling relationships, but, instead of a single scaling temperature TC as found for supercooled liquids, in the liquid crystals there are two scaling temperatures TCL (L for low temperature) and TCH (H for high temperature). TCH is very close to T*, which results from LdG scaling, just below the isotropic to nematic phase transition temperature, TNI, but is 30–50 K higher than TCL. The liquid crystal time dependent data have the identical functional form as supercooled liquid data, that is, a fast power law decay with temperature independent exponent, followed by a slower power law decay with temperature independent exponent, and on the longest time scales, an exponential decay with highly temperature dependent decay constant. For each liquid crystal, the amplitudes of the two power laws scale with expressions that involve TCL, but the exponential decay time constant (long time dynamics) scales with an expression that involves TCH. The existence of two scaling temperatures can be interpreted as a signature of two “glass transitions” in liquid crystals. In ideal MCT developed for spheres, TC is the “ideal glass transition temperature,” although it is found experimentally to be ∼20%–30% above the experimental glass transition temperature, Tg. The transition in nematic liquid crystals at TCL corresponds to the conventional ideal MCT glass transition, while the transition at TCH can occur for nonspherical molecules, and may correspond to the freezing in of local nematic order.