Found in our recent dielectric study of a planar and rigid glass-former, 1-methylindole (1MID), is an unusual secondary relaxation unrelated in its dynamic properties to the structural α-relaxation. We speculated that it originates from the in-plane motion of the molecules, and the supposedly universal Johari-Goldstein (JG) β-relaxation with strong connection to the structural α-relaxation in rigid glass-formers is not resolved [X. Q. Li et al. J. Chem. Phys. 143, 104505 (2015)]. In this work, dielectric measurements are performed in binary mixtures of 1MID with two aromatics of weak polarity, ethylbenzene (EB) and triphenylethylene (TPE), in the highly viscous regimes near glass transition. EB and TPE have smaller and larger molecular sizes and glass transition temperatures T than 1MID, respectively. Strikingly, the results show that the resolved secondary relaxations of 1MID in the two mixtures share the same relaxation time and their temperature dependence as pure 1MID, independent of the mode and degree of dilution. The results indicate that the unusual secondary relaxation is not directly coupled with the α-relaxation, and support the in-plane-rotation interpretation of its origin. On the other hand, the supposedly universal and intermolecular JG β-relaxation coming from the out-of-plane motion of the planar molecule has weaker dielectric strength, and it cannot be resolved from the more intense in-plane-rotation secondary relaxation because the dipole moment of 1MID lies on the plane.

Two glass-transitions have been observed in some miscible molecular mixtures with notable difference in geometry or chemistry of constituents. Explanation of the phenomena has been puzzling with diverse structural models....

In our recent study [T. Wu et al., J. Chem. Phys. 147, 134501 (2017)], an alkyl phosphate glass former was studied and it suggested that the enthalpy relaxation involving the motions of all parts of the molecule is global, while the dielectric relaxation detects the local rotation of the polar core. In this work, we study a series of trialkyl phosphates using calorimetric and dielectric measurements over a wide temperature range. The results indicate a departure of the dielectric fragility indexes from the enthalpic ones as the length of the branch chain increases in the trialkyl phosphates. The Kirkwood correlation factor (gk) is found to coincide at ∼0.6 at glass transition temperature (Tg) from triethyl phosphate to tributyl phosphate, indicating a similar structural alignment. The enthalpic relaxation serving as the more fundamental relaxation relevant to the structural relaxation is confirmed. Strikingly, we observed the relation of Tg to the chain length in alkyl phosphates, revealing a minimum Tg behavior, and its explanation assists in the understanding of the glass transition in relation to the structure of the glass-formers.

The dielectric spectra of methyl m-toluate (MMT) in supercooled liquid and glassy states were measured over wide ranges of temperature T at ambient and elevated pressures P. We found that the frequency dispersion of the loss peak contributed by the structural α-relaxation is invariant to changes of P and T, while keeping the loss peak frequency f α(T,P) constant. This isochronal superposition property of the α-relaxation holds for different choices of f α(T,P). The invariant frequency dispersions for the same f α(T,P) are also indicated by the fractional exponent βKWW in the Fourier transform of the Kohlrausch–Williams–Watts (KWW) function. Similarly, the fragility m index of MMT keeps approximately constant on varying pressure, largely different from H-bonded glass formers. The secondary β-relaxation at a frequency higher than f α(T,P) is found to shift to lower frequencies by elevating pressure in concert with the α-relaxation. The ratio τα(T,P)/τβ(T,P) is approximately unchanged to variations of T and P while keeping τα(T,P) constant. These properties observed in MMT offer experimental evidence of the dynamic correlation between α- and β-relaxations in pure small-molecule glass-formers.

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