Translational and reorientational dynamics in deep eutectic solvents

TL;DR

This study investigates the complex translational and reorientational dynamics of deep eutectic solvents across broad temperature ranges, revealing coupled motions in some DESs and decoupled ionic transport in others, challenging previous mechanisms.

Contribution

It provides a comprehensive analysis of the dynamic behaviors of DESs using rheological and dielectric spectroscopy, highlighting differences in ionic and molecular motions and challenging existing charge-transport models.

Findings

Glyceline and ethaline show coupled ionic and molecular dynamics.

Reeline exhibits decoupled ionic transport with enhanced low-temperature conductivity.

The random free-energy barrier hopping model describes compliance spectra well.

Abstract

We performed rheological measurements of the typical deep eutectic solvents (DESs) glyceline, ethaline, and reline in a very broad temperature and dynamic range, extending from the low-viscosity to the high-viscosity supercooled-liquid regime. We find that the mechanical compliance spectra can be well described by the random free-energy barrier hopping model, while the dielectric spectra on the same materials involve significant contributions arising from reorientational dynamics. The temperature-dependent viscosity and structural relaxation time, revealing non-Arrhenius behavior typical for glassy freezing, are compared to the ionic dc conductivity and relaxation times determined by broadband dielectric spectroscopy. For glyceline and ethaline we find essentially identical temperature dependences for all dynamic quantities. These findings point to a close coupling of the ionic and molecular translational and reorientational motions in these systems. However, for reline the ionic charge transport appears decoupled from the structural and reorientational dynamics, following a fractional Walden rule. Especially, at low temperatures the ionic conductivity in this DES is enhanced by about one decade compared to expectations based on the temperature dependence of the viscosity. The results for all three DESs can be understood without invoking a revolving-door mechanism previously considered as a possible charge-transport mechanism in DESs.