Multimodal character of shear viscosity response in hydrogen bonded liquids

Abstract

The impact of supramolecular aggregate formation on the shear viscosity response of hydrogen bonded liquids was investigated. In particular, we study the shear mechanical response of several monoalcohols showing exponential and non-exponential shape dielectric Debye-like relaxation. In addition to the structural relaxation, distinctive of the glass transition, and the terminal crossover to pure viscous flow, characteristic of simple liquid flow, systematic analysis of complex viscosity curves evidences the presence of an additional intermediate process between those two. While the recovery of pure viscous flow would reflect the complete relaxation of the hydrogen bonded aggregates the intermediate process correlates with the rotational dynamics of hydroxyl groups, potentially caused by the breaking of individual hydrogen bonds.