New paradigm of dielectric relaxation of sizable and rigid molecular glass formers.

ABSTRACT

In this Rapid Communication we report the unusual dynamics of planar, rigid, and anisotropy glass-forming molecules of unusually large size by dielectric spectroscopy by using two examples. The size of the molecules is much larger than the dipolar moiety located at the end of the longer axis of each molecule. The observed dynamics deviates strongly from the anticorrelation between ß_{KWW} (fractional exponent of the Kohlrausch-Williams-Watts function) and dielectric strength, Δɛ(T_{g}), established generally for small van der Waals molecular glass formers. Moreover, the dynamics of the two large molecules differ greatly, albeit the difference is the dipole moment being orthogonal or parallel to the longer axis of the molecules. The drastic variation in dielectric response of the two materials coming from different portions of the structural α-relaxation spectrum is probed by the dipole. Thus, the new behavior opens up a new research area of the dynamics and thermodynamics of nonpolymeric sizable molecules, the dielectric response of which can be varied by the design of the dipole moiety.