Dynamics of glass-forming liquids. XX. Third harmonic experiments of non-linear dielectric effects versus a phenomenological model

We have re-measured the third harmonic non-linear dielectric response of supercooled glycerol using zero-bias sinusoidal electric fields, with the aim of comparing the resulting susceptibilities with a phenomenological model of non-linear dielectric responses. In the absence of known chemical effects in this liquid, the present model accounts for three sources of non-linear behavior: dielectric saturation, field induced entropy reduction, and energy absorption from the time dependent field. Using parameters obtained from static high field results, the present model reproduces the characteristic features observed in the third harmonic susceptibility spectra: a low frequency plateau originating from dielectric saturation and a peak positioned below the loss peak frequency whose amplitude increases with decreasing temperature. Semi-quantitative agreement is achieved between experiment and the present model, which does not involve spatial scales or dynamical correlations explicitly. By calculating the three contributions separately, the model reveals that the entropy effect is the main source of the "hump" feature of this third harmonic response.