Viscoelastic relaxations of high alcohols and alkanes: Effects of heterogeneous structure and translation-orientation coupling

Abstract

The frequency-dependent shear viscosity of high alcohols and linear alkanes, including 1-butanol, 1-octanol, 1-dodecanol, n-hexane, n-decane, and n-tetradecane, was calculated using molecular dynamics simulation. The relaxation of all the liquids was bimodal. The correlation functions of the collective orientation were also evaluated. The analysis of these functions showed that the slower relaxation mode of alkanes is assigned to the translation-orientation coupling, while that of high alcohols is not. The X-ray structure factors of all the alcohols showed prepeaks, as have been reported in the literature, and the intermediate scattering functions were calculated at the prepeak. Comparing the intermediate scattering function with the frequency-dependent shear viscosity based on the mode-coupling theory, it was demonstrated that the slower viscoelastic relaxation of the alcohols is assigned to the relaxation of the heterogeneous structure described by the prepeak.