Insights on the origin of the Debye process in monoalcohols from dielectric spectroscopy under extreme pressure conditions

Abstract

The dielectric spectra of most simple liquids are characterized by two relaxation processes: (i) the alpha-process, an intense, broad non-Debye relaxation with a non-Arrhenius temperature dependence and (ii) a beta process, evident mainly below the glass transition and having nearly Arrhenius temperature behavior. However, the dielectric spectra of monoalcohols show three processes: two that resemble those of normal liquids and a third very intense Debye peak at lower frequencies, which is non-Arrhenius. Interestingly, this third process is not observed with other techniques such as light scattering and mechanical spectroscopy. There is a disagreement in the literature concerning the nature of this third relaxation. We investigated 2-ethyl-1-hexanol under high pressures (up to approximately 1.4 GPa) over a broad range of temperatures. The Debye process, which is the slowest, is strongly affected by pressure. At higher pressures the relaxation times and intensities of the two non-Arrhenius relaxations become more nearly equal. In light of these results, we propose a modified interpretation of the relaxation processes and their underlying structures in monoalcohols.