Nonlinear dielectric features of highly polar glass formers: Derivatives of propylene carbonate

We have measured the nonlinear dielectric behavior of several highly polar propylene carbonate (PC) derivatives in the vicinity of their glass transition temperatures. Focus is on the effects of a large static electric field on the frequency dependent permittivity and on the cubic susceptibility measured using sinusoidal fields of high amplitude. The case of vinyl-PC shows dielectric saturation as well as an electro-rheological effect, i.e., a field induced increase of dielectric relaxation times, whose magnitude changes linearly with the apparent activation energy. The extent of this shift of the loss profile caused by the field correlates strongly with the peak magnitude of the cubic susceptibility, |χ₃|, underlining the notion of a link between the |χ₃| "hump" and this electro-rheological behavior. Further support for this picture emerges from the observation that the most polar of these liquids, (S)-(-)-methoxy-PC with ε_s ≈ 250, lacks both the electro-rheological effect in ε″(ω) and the "hump" typically observed in |χ₃(ω)|. The absence of any sensitivity of the dynamics to an electric field is contrary to the expectation that the electro-rheological effect correlates with the field induced entropy change, which is extraordinarily high for this liquid. The results suggest that the dependence of the relaxation time on the electric field is not directly linked to the entropy change.