Orientation polarization from faster motions in the ultraviscous and glassy diethyl phthalate and its entropy
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Dielectric spectra of the beta relaxation in glassy and ultraviscous liquid diethyl phthalate show that its relaxation strength Delta epsilon(beta), the distribution of times, and the relaxation rate are more sensitive to temperature T in the ultraviscous liquid than in the glassy state. The Delta epsilon(beta) against temperature plot has an elbow-shaped break near T(g) of approximately 181 K, which is remarkably similar to that observed in the entropy, enthalpy, and volume against temperature plots, and in the plot of Delta epsilon(beta) against the liquid's entropy minus its 0 K value. The ratio of Delta epsilon(beta) to diethyl phthalate's entropy, after subtracting the 0 K value, is 1.08 x 10(-3) mol K/J in the glassy state at 120.4 K, which decreases slowly to 0.81 x 10(-3) mol K/J at 176 K near T(g) and thereafter rapidly increases to 1.57 x 10(-3) mol K/J at 190 K. Variation in Delta epsilon(beta) parallels the variation of the entropy. A change in the activation energy of the beta process at T>T(g) indicates that its rate is also determined by the structure of the ultraviscous liquid. Features of beta relaxation are consistent with localized motions of molecules and may not involve small-angle motions of all molecules.
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