We have performed a thorough examination of the reorientational relaxation dynamics and the ionic charge transport of three typical deep eutectic solvents, ethaline, glyceline and reline, by using broadband dielectric spectroscopy. Our experiments cover a broad temperature range from the low-viscosity liquid down to the deeply supercooled state, allowing us to investigate the significant influence of glassy freezing on the ionic charge transport in these systems. In addition, we provide evidence for a close coupling of the ionic conductivity in these materials to reorientational dipolar motions, which should be considered when searching for deep eutectic solvents optimized for electrochemical applications.

Ionic conductivity of deep eutectic solvents: the role of orientational dynamics and glassy freezing.

This article gives an overview of experimental results on dynamics in bulk glass-forming molecular liquids. Rather than looking for phenomenology that is universal, in the sense that it is seen in all liquids, the focus is on identifying the basic characteristics, or "stylized facts," of the glass transition problem, i.e., the central observations that a theory of the physics of glass formation should aim to explain in a unified manner.

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Perspective: Searching for simplicity rather than universality in glass-forming liquids.

Abstract Nanoparticles (NPs) of Gd1−xMxCrO3 (M = La, Co, Bi) were synthesized by microemulsion techniques, involving simultaneous single ion substitution philosophy. Structural, magnetic, dielectric properties, morphology, elemental analysis and distribution size of fabricated nano-crystalline were determined. The techniques employed for investigation are X-ray diffraction (XRD), vibrating sample magnetometer (VSM), dielectric measurement and scanning electron microscopy (SEM), energy dispersive X-ray (EDX), photoluminescence (PL) and atomic force microscopy (AFM), respectively. XRD pattern confirm that all the as-synthesized NPs have orthorhombic structure and successfully substituted of different metal ions into the regular crystal structure of GdCrO3. The lattice parameters X-ray density, bulk density, porosity and grain size were calculated from XRD pattern of Gd1−xMxCrO3 (M = La, Co, Bi) substituted and un-substituted GdCrO3. The magnetic hysteresis loop of fabricated product confirmed that the entire sample exhibits ferromagnetic behavior at room temperature. It was also found that the fabricated NPs show excellent photocatalytic activity (PCA) against Congo-red, about 78.24% after 55 min of incubation.

Structural, Dielectric and Magnetic Studies of Perovskite [Gd1−xMxCrO3 (M = La, Co, Bi)] Nanoparticles: Photocatalytic Degradation of Dyes

The slow Debye-like relaxation in the dielectric spectra of monohydroxy alcohols is a matter of long-standing debate. In the present Letter, we probe reorientational dynamics of 5-methyl-2-hexanol with dielectric spectroscopy and depolarized dynamic light scattering (DDLS) in the supercooled regime. While in a previous study of a primary alcohol no indication of the Debye peak in the DDLS spectra was found, we now for the first time report clear evidence of a Debye contribution in a monoalcohol in DDLS. A quantitative comparison between the dielectric and DDLS manifestation of the Debye peak reveals that while the dielectric Debye process represents fluctuations in the end-to-end vector dipole moment of the transient chains, its occurrence in DDLS shows a more local signature and is related to residual correlations that occur due to a slight anisotropy of the $\ensuremath{\alpha}$ relaxation caused by the chain formation.

Nature of the Debye-Process in Monohydroxy Alcohols: 5-Methyl-2-Hexanol Investigated by Depolarized Light Scattering and Dielectric Spectroscopy.

We present a detailed comparison of the microscopic dynamics and the macroscopic mechanical behavior of novel butyl rubber ionomers with tunable dynamics of sparse sticky imidazole-based sidegroups...

Hierarchical Sticker and Sticky Chain Dynamics in Self-Healing Butyl Rubber Ionomers

One of the unsolved problems of dynamics in supercooled liquids are the differences in spectral shape of the structural relaxation observed among different methods and substances, and a possible generic line shape has long been debated. We show that the light scattering spectra of very different systems, e.g., hydrogen bonding, van der Waals liquids, and ionic systems, almost perfectly superimpose and show a generic line shape of the structural relaxation, following ∝ ω-1/2 at high frequencies. In dielectric spectra the generic behavior is recovered only for systems with low dipole moment, while in strongly dipolar liquids additional cross-correlation contributions mask the generic structural relaxation.

Generic Structural Relaxation in Supercooled Liquids.

We suggest a way to disentangle self- from cross-correlation contributions in the dielectric spectra of glycerol. Recently it was demonstrated for monohydroxy alcohols that a detailed comparison of the dynamic susceptibilities of photon correlation and broadband dielectric spectroscopy allows to unambiguously disentangle a collective relaxation mode known as the Debye process, which arises due to supramolecular structures, and the α-relaxation, which proves to be identical in both methods. In the present paper, we apply the same idea and analysis to the paradigmatic glass former glycerol. For that purpose we present new light scattering data from photon correlation spectroscopy measurements and combine these with literature data to obtain a data set covering a dynamic range from 10−4–1013 Hz. Then we apply the above mentioned analysis by comparing this data set with a corresponding set of broadband dielectric data. Our finding is that even in a polyalcohol self- and cross-correlation contributions can approximately be disentangled in that way and that the emerging picture is very similar to that in monohydroxy alcohols. This is further supported by comparing the data with fast field cycling NMR measurements and dynamic shear relaxation data from the literature, and it turns out that, within the described approach, the α-process appears very similar in all methods, while the pronounced differences observed in the spectral density are due to a different expression of the slow collective relaxational contribution. In the dielectric spectra the strength of this peak is reasonably well estimated by the Kirkwood correlation factor, which supports the view that it arises due to dynamic cross-correlations, which were previously often assumed to be negligible in dielectric measurements.

Intermolecular cross-correlations in the dielectric response of glycerol.

The nonexponential shape of the α process observed in supercooled liquids is considered as one of the hallmarks of glassy dynamics and has thus been under study for decades, but is still poorly understood. For a polar van der Waals liquid, we show here-in line with a recent theory-that dipole-dipole correlations give rise to an additional process in the dielectric spectrum slightly slower than the α relaxation, which renders the resulting combined peak narrower than observed by other experimental techniques. This is reminiscent of the Debye-process found in monohydroxy alcohols. The additional peak can be suppressed by weakening the dipole-dipole interaction via dilution with a nonpolar solvent.

Dipole-dipole correlations and the Debye process in the dielectric response of nonassociating glass forming liquids.

We investigate molecular dynamics of two supercooled room temperature ionic liquids (RTILs) above of their glass transition temperature by means of dynamic light scattering and broadband dielectric spectroscopy from nanoseconds up to ≈ 10 5 s . We show that a direct comparison of the raw data of these two techniques allows us to identify the reorientation of ions in the dielectric data, giving experimental evidence to a very recently proposed model of Gainaru et al. [1] , stating that the conductivity process in ionic liquids takes place through a reorientational step of ions escaping their cage formed by surrounding counterions. Within this approach we can also understand the apparent decoupling of time constants from dielectric spectroscopy and light scattering, often found in ionic liquids, in a very natural way. Furthermore, as a consequence of knowing the reorientational part of the dielectric spectrum, we are able to show that two more processes contribute to these spectra, which are due to electrode polarization effects. The relative position of all three contributions vary among the systems and may overshadow each other, thus complicating the data analysis and favor misinterpretations.

Molecular dynamics of supercooled ionic liquids studied by light scattering and dielectric spectroscopy

The dielectric Debye relaxation in monohydroxy alcohols has been subject of long-standing scientific interest and is presently believed to arise from the relaxation of transiently H-bonded supramolecular structures. Therefore, its manifestation in a measurement with a local dielectric probe might be expected to be different from the standard macroscopic dielectric experiment. In this work we present such local dielectric measurements obtained by triplet state solvation dynamics (TSD) and compare the results with macroscopic dielectric and light scattering data. In particular, with data from an improved TSD setup, a detailed quantitative comparison reveals that the Debye process does not significantly contribute to the local Stokes shift response function, while α- and β-relaxations are clearly resolved. Furthermore, this comparison reveals that the structural relaxation has almost identical time constants and shape parameters in all three measurement techniques. Altogether our findings support the notion that the transiently bound chain structures lead to a strong cross-correlation contribution in macroscopic dielectric experiments, to which both light scattering and TSD are insensitive, the latter due to its local character and the former due to the molecular optical anisotropy being largely independent of the OH bonded suprastructures.

Peter Weigl

Papers

Generic Structural Relaxation in Supercooled Liquids.

Intermolecular cross-correlations in the dielectric response of glycerol.

Dipole-dipole correlations and the Debye process in the dielectric response of nonassociating glass forming liquids.

Molecular dynamics of supercooled ionic liquids studied by light scattering and dielectric spectroscopy

Local dielectric response in 1-propanol: α-relaxation versus relaxation of mesoscale structures.