Appearance of a Debye process at the conductivity relaxation frequency of a viscous liquid

J Chem Phys. 2011 Mar 14;134(10):104508. doi: 10.1063/1.3565481.

Abstract

The existence of a Debye-type ultraslow process in dielectric spectra of bulk polyalcohols and similar materials has been reported repeatedly in the recent literature. Its loss peak is observed at frequencies that are decades below those of the primary structural relaxation, in a range where the loss signal is usually dominated by dc-conductivity or even electrode polarization. We show that this peak originates from an incomplete filling of the capacitor volume, e.g., as a result of gas bubbles, a situation that gives rise to a Debye process at the conductivity relaxation frequency of the material, where the values of storage and loss components of permittivity are identical. The result implies that these peaks are not endemic to the liquid and can lead to various misinterpretations of the dielectric relaxation spectra. Techniques avoiding the occurrence of such artifacts are discussed.