Deviations of dynamic parameters characterizing enthalpic and dielectric relaxations in glass forming alkyl phosphates.

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 (g k ) is found to coincide at ∼0.6 at glass transition temperature (T g ) 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 T g to the chain length in alkyl phosphates, revealing a minimum T g behavior, and its explanation assists in the understanding of the glass transition in relation to the structure of the glass-formers.