On the temperature and pressure dependence of dielectric relaxation processes in ionic liquids

Molecular dynamics of ionic liquids in an electric field can be decomposed into contributions from translational motions of ions, rotational motions of permanent dipoles and - in the case of ions equipped with long alkyl-chains - motions of ionic aggregates. The discrimination of these contributions in the dielectric spectrum is quite involved, resulting in numerous controversies in the literature. Here, we use dielectric spectroscopy at ambient and elevated pressures of up to 550 MPa to monitor the changes of the observed processes in five supercooled ionic liquids with octyl-chains independent of pressure and temperature. In most of the ionic liquids under investigation two dynamical processes are observed, one of them is identified as the ion hopping process, which we describe by the MIGRATION model. It turns out that this process is closely connected to the glass transition step as measured by differential scanning calorimetry. Concerning the second process, we rule out motions of aggregated ions to be its origin by comparison of our results with X-ray scattering literature data at elevated pressure. Instead, we tentatively ascribe it to dipolar reorientations and show that the dielectric strength of this slow process decreases as a function of increasing relaxation time, i.e. for decreasing temperatures and increasing pressures. We compare this behavior with literature data of other ion conducting systems and discuss its microscopic origin. The temperature and pressure dependence of two dynamic processes in the dielectric spectra of five supercooled ionic liquids equipped with octyl-chains are reported. The microscopic origin of these processes is discussed.