Nonlinear dielectric effects in liquids: A guided tour

Dielectric relaxation measurements probe how the polarization of a material responds to the application of an external electric field, providing information on structure and dynamics of the sample. In the limit of small fields and thus linear response, such experiments reveal the properties of the material in the same thermodynamic state it would have in the absence of the external field. At sufficiently high fields, reversible changes in enthalpy and entropy of the system occur even at constant temperature, and these will in turn alter the polarization responses. The resulting nonlinear dielectric effects feature field induced suppressions (saturation) and enhancements (chemical effect) of the amplitudes, as well as time constant shifts towards faster (energy absorption) and slower (entropy reduction) dynamics. This review focuses on the effects of high electric fields that are reversible and observed at constant temperature for single component glass-forming liquids. The experimental challenges involved in nonlinear dielectric experiments, the approaches to separating and identifying the different sources of nonlinear behavior, and the current understanding of how high electric fields affect dielectric materials will be discussed. Covering studies from Debye's initial approach to the present state-of-the-art, it will be emphasized what insight can be gained from the nonlinear responses that are not available from dielectric relaxation results obtained in the linear regime.