For more than 100 years, melting has been thought to be governed by the Lindemann criterion, which assumes that a crystal melts when, upon heating, the growing atomic vibration amplitudes become sufficiently large to destabilize its crystalline lattice. However, it is unclear why the viscosities eta or the related relaxation times tau of the resulting liquids, measured directly at the melting point Tm, differ by up to nine decades, depending on the material. Based on the empirical rule that the ratio of the glass-transition temperature and Tm is about 2/3, here we show that this strong variation is due to differences in the liquid's fragilities, a property associated with pronounced non-Arrhenius behavior and often ascribed to cooperative motions. We propose that, without cooperativity, all crystals would melt into liquids with a universal viscosity value and relaxation time. Hence, the real melting point is only partly determined by the Lindemann criterion and is strongly enhanced by the cooperativity of the resulting liquid. Our findings are corroborated by the determination of the idealized, fragilityfree melting temperatures and of the corresponding eta and tau values for various example materials.

In the present work, we examine the relevance and proper interpretation of broadband-dielectric and THz-spectroscopy data for the investigation of various types of biological matter. We provide an overview of the rich variety of different dynamic processes that can be detected by these experimental methods. Several experimental examples are discussed in detail, helping to understand the information that can be drawn from such studies. This includes dielectric spectra, extending well into the GHz region, for pure water, which can be considered as a simple but highly important biological molecule. We also discuss results for a prototypical aqueous solution of a protein, belonging to one of the most important classes of biological macromolecules. Moreover, we examine broadband dielectric spectra on blood as an example of functional biological matter in organisms. To demonstrate the relevance of THz spectroscopy for the investigation of biological molecules, we finally treat such experiments applied to different amino acids.

Since more than 100 years, melting is thought to be governed by the Lindemann criterion. It assumes that a crystal melts when, upon heating, the growing atomic vibration amplitudes become sufficiently large to destabilize its crystalline lattice. However, it is unclear why the viscosities eta or the related relaxation times tau of the resulting liquids, measured directly at the melting point Tm, differ by up to nine decades, depending on the material. Based on the empirical rule that the ratio of the glass-transition temperature and Tm is about 2/3, here we show that this strong variation is due to differences in the liquid's fragilities, a property associated with pronounced non-Arrhenius behavior and often ascribed to cooperative motions. We propose that, without cooperativity, all crystals would melt into liquids with a universal viscosity value and relaxation time. Hence, the real melting point is only partly determined by the Lindemann criterion and strongly enhanced by the cooperativity of the resulting liquid. Our findings are corroborated by the determination of the idealized, fragility-free melting temperatures, and of the corresponding eta and tau values for various example materials.

Translational dielectric loss peaks and multinuclear magnetic resonance permit quantitative insights into the dynamic coupling of Li ion conductors.

A detailed study of published experimental data for a variety of materials on the incremental variation of heat capacity, thermal expansion, and compressibility at glassy freezing reveals a striking dependence of the Prigogine-Defay ratio R on the fragility index m. At high m, R approaches values of ∼1, the Ehrenfest expectation for second-order continuous phase transitions, while R reaches values >20 for low fragilities. We explain this correlation by the degree of separation of the glassy freezing temperature from a hidden phase transition into an ideal low-temperature glass.

In conventional ferroelectrics, the electric dipoles are generated by off-center displacements of ions or by the ordering of dipolar molecular units. In recent years, a new type of so-called electronic ferroelectrics has attracted great attention, where the polarization is driven by electronic degrees of freedom. Of particular interest are materials with strong electronic correlations, featuring a variety of intriguing phenomena and instabilities, which may interact with or even induce electronic ferroelectricity. In this review, we will focus on the class of strongly correlated charge-transfer salts, where electronic ferroelectricity was suggested by theory and has been confirmed by numerous experiments. The paper summarizes some basic physical properties of various relevant quasi-two-dimensional salts and gives some background on the experimental tools applied to establish ferroelectricity. We discuss the key experimental observations, including the exciting discovery of multiferroicity, and provide some theoretical considerations on the magnetoelectric couplings that are of relevance here.

Poly(ethylene oxide) is an important polymer with many applications, e.g., as solid-state electrolyte in batteries. Its relaxation dynamics, characterizing its molecular and submolecular motions, which is relevant for many of these applications, was investigated numerous times, mostly employing dielectric spectroscopy. However, the various dynamic processes revealed by these studies were interpreted in conflicting ways and even their nomenclature in literature is highly inconsistent. Here we present the results of a detailed investigation of this polymer employing dielectric spectroscopy covering a relatively broad frequency and temperature range. We clearly detect four intrinsic relaxation processes. The slowest one most likely represents a so-called normal mode, reflecting global motions of the polymer chains, an interpretation that was not considered in previous works. The second process can be unequivocally identified with the segmental alpha relaxation, which governs glassy freezing and the glass transition. The third, only rarely detected process corresponds to the Johari-Goldstein relaxation of poly(ethylene oxide), widely overlooked in previous studies. The fourth and fastest process is unrelated to the supercooled and glassy state of this polymer and probably due to local, intramolecular motions.

The investigation of water's glass transition and a possible liquid-liquid transition within its supercooled state is hampered by its inevitable crystallization in a temperature range, termed "no-man's land." Here we report dielectric-spectroscopy and calorimetry measurements of pure water and various aqueous LiCl solutions, part of the latter being quenched to avoid crystallization. By investigating solutions of relatively low salt content and by covering an exceptionally broad frequency range up to THz, we find strong hints at a crossover in water from a strong to a fragile liquid, characterized by different glass-transition temperatures and different non-Arrhenius temperature dependencies of the molecular dynamics.

Recently, a universal relation between the thermal expansion coefficient of glasses $\alpha_g$, their glass-transition temperature Tg, and the so-called fragility index m of the corresponding supercooled liquid state was found to be valid for more than 200 glass formers, namely $\alpha_g/m\propto 1/T_g$ [P. Lunkenheimer et al., Nat. Phys. 19, 694 (2023)]. Here we show that this could also have far-reaching consequences for our understanding of crystal melting. Namely, when considering the empirically founded 2/3-rule, stating that the ratio of Tg and the melting temperature Tm is about 2/3 for almost all materials, for crystals a similar relation, $\alpha_c/m\propto 1/T_m$, should apply. Indeed, we find that the available experimental data are well consistent with such a relation. This implies that the melting of a crystal into an ordinary (non-supercooled) liquid is influenced by the fragility, a property quantifying the non-Arrhenius dynamics in the supercooled-liquid state of the material. We argue that this can be explained by a significant enhancement of the "ideal" (non-cooperative) melting temperature arising from the cooperativity of the particle motion in the liquid state above Tm. Therefore, a reassessment of the currently widely accepted microscopic understanding of crystal melting, still founded on the general ideas that lead to the time-honored Lindemann melting criterion, may be necessary.

A promising mechanism for achieving colossal dielectric constants involves the use of insulating internal barrier layers, such as insulating domain walls in ferroelectrics. A key advantage of domain walls, compared to other stationary interfaces, is their mobility, offering the potential for post-synthesis adjustment of the dielectric constant. In this work, we demonstrate that altering the domain wall density enables the tuning of the dielectric constant in our template material, i.e., hexagonal ErMnO3 single crystals. Through microscopy and macroscopic dielectric spectroscopy, we quantify changes in domain wall density and correlated these with changes in dielectric constant within a single sample. Analysis of the dielectric data suggests that the insulating domain walls act as “ideal” capacitors connected in series. Our approach to engineering the domain wall density can be readily extended to other control methods, e.g., electric fields or mechanical stresses, providing a degree of flexibility to in situ tune the dielectric constant.

Ferroelectricity, where electronic degrees of freedom determine the polar order—thereby enabling fast switching and phase control—is an important research field in current condensed-matter physics. Using a combination of resistance noise and dielectric spectroscopy we investigate the nature of relaxor-type electronic ferroelectricity in the organic conductor κ-(BETS)2Mn[N(CN)2]3, a system that represents a wider class of materials of correlated electron systems for which functionalities for organic spintronics recently have been discussed. The two complementary spectroscopies reveal a distinct low-frequency dynamics on different length scales, namely (i) an intrinsic relaxation that is typical for relaxor ferroelectrics which classifies the system as a possible new multiferroic, and (ii) two-level processes which we identify as fluctuating polar nanoregions (PNR), i.e., clusters of quantum electric dipoles that fluctuate collectively. The PNR preform above the metal insulator (MI) transition. Upon cooling through TMI, a drastic increase of the low-frequency 1/f-type fluctuations and slowing down of the charge carrier dynamics is accompanied by the onset of strong non-equilibrium dynamics indicating a glassy transition of interacting dipolar clusters. The freezing of PNR and non-equilibrium dynamics is suggested to be a common feature of organic relaxor-type electronic ferroelectrics.

Glass formation and reorientational motions are widespread, but often-neglected features of deep eutectic solvents, although both can be relevant for the technically important ionic conductivity at room temperature. Here we investigate these properties for two mixtures of ethylene glycol and ZnCl2, which were recently considered as superior electrolyte materials for application in zinc-ion batteries. For this purpose, we employed dielectric spectroscopy performed in a broad temperature range, extending from the supercooled state at low temperatures up to the liquid phase around room temperature and beyond. We find evidence for a relaxation process arising from dipolar reorientation dynamics, which reveals the clear signatures of glassy freezing. This freezing also governs the temperature dependence of the ionic dc conductivity. We compare the obtained results with those for deep eutectic solvents that are formed by the same hydrogen-bond donor, ethylene glycol, but by two different salts, choline chloride and lithium triflate. The four materials reveal significantly different ionic and reorientational dynamics. Moreover, we find varying degrees of decoupling of rotational dipolar and translational ionic motions, which partly can be described by a fractional Debye-Stokes-Einstein relation. The typical glass-forming properties of these solvents strongly affect their room-temperature conductivity.

Deep eutectic solvents with admixed lithium salts are considered as electrolytes in electrochemical devices, such as batteries or supercapacitors. Compared to eutectic mixtures of hydrogen-bond donors and lithium salts, their raw-material costs are significantly lower. Not much is known about glassy freezing and rotational-translation coupling of such systems. Here, we investigate these phenomena by applying dielectric spectroscopy to the widely studied deep eutectic solvent glyceline, to which 1 and 5 mol % LiCl were added. Our study covers a wide temperature range, including a deeply supercooled state. The temperature dependences of the detected dipolar reorientation dynamics and ionic direct current (dc) conductivity reveal the signatures of glassy freezing. In comparison to pure glyceline, the lithium admixture leads to a reduction of ionic conductivity, which is accompanied by a reduction of the rotational dipolar mobility. However, this reduction is much smaller than that for deep eutectic solvents (DESs), where one main component is lithium salt, which we trace back to the lower glass-transition temperatures of lithium-doped DESs. In contrast to pure glyceline, the ionic and dipolar dynamics become increasingly decoupled at low temperatures and obey a fractional Debye-Stokes-Einstein relation, as previously found in other glass-forming liquids. The obtained results demonstrate the relevance of decoupling effects and glass transition to the enhancement of the technically relevant ionic conductivity in such lithium-doped DESs.

The present study examines the potential coupling between dipolar dynamics and ionic charge transport in metal-organic framework (MOF) compounds. MOFs are known for their high porosity and customizable properties. By integrating freely rotating dipolar groups into the ligands, a novel structure, CFA-25, akin to the known BUT-2 framework, is synthesized. This facilitated the investigation of local and macroscopic effects, particularly the possible interplay between dipolar units and Cs cations. The research aimed to understand fundamental dipolar dynamics and ionic charge transport, employing Cs ions for their X-ray diffraction characterizability. Experimental analysis using dielectric spectroscopy, complemented by theoretical simulations, explored questions regarding glassy freezing of re-orientational dynamics, Cs cation motion within the network, and the influence of dipolar units on transport. Contrary to previous reports, this work finds that Cs transport exhibits substantial barriers, necessitating specialized simulation techniques for accurate characterization. This interdisciplinary approach sheds light on the intricate dynamics of MOFs and offers insights into their potential applications involving ion transport phenomena.

The glass formation and the dipolar reorientational motions in deep eutectic solvents (DESs) are frequently overlooked, despite their crucial role in defining the room-temperature physiochemical properties. To understand the effects of these dynamics on the ionic conductivity and their relation to the mechanical properties of the DES, we conducted broadband dielectric and rheological spectroscopy over a wide temperature range on three well-established carboxylic acid-based natural DESs. These are the eutectic mixtures of choline chloride with oxalic acid (oxaline), malonic acid (maline), and phenylacetic acid (phenylaceline). In all three DESs, we observe signs of a glass transition in the temperature dependence of their dipolar reorientational and structural dynamics, as well as varying degrees of motional decoupling between the different observed dynamics. Maline and oxaline display a breaking of the Walden rule near the glass-transition temperature, while the relation between the dc conductivity and dipolar relaxation time in both maline and phenylaceline is best described by a power law. The glass-forming properties of the investigated systems not only govern the orientational dipolar motions and rheological properties, which are of interest from a fundamental point of view, but they also affect the dc conductivity, even at room temperature, which is of high technical relevance.

We present a detailed study on the temperature-dependent THz spectra of the polycrystalline amino acids, L-serine and L-cysteine, for wavenumbers from 20 to 120 cm-1 and temperatures from 4 to 300 K. Even though the structure of these two amino acids is very similar, with a sulfur atom in the side chain of cysteine instead of an oxygen atom in serine, the excitation spectra are drastically different. Obviously, the vibrational dynamics strongly depend on the ability of cysteine to form sulfur-hydrogen bonds. In addition, cysteine undergoes an order-disorder type phase transition close to 80 K, documented by additional specific heat experiments, with accompanying anomalies in the THz results. On increasing temperatures, well-defined vibrational excitations exhibit significant shifts in the eigenfrequencies with concomitant line-broadening yielding partly overlapping modes. Interestingly, several modes completely lose all their dipolar strength and are unobservable under ambient conditions. Comparing the recent results to the published work utilizing THz, Raman, and neutron-scattering techniques, as well as with ab initio simulations, we aim at a consistent analysis of the results ascribing certain eigenfrequencies to distinct collective lattice modes. We document that THz spectra can be used to fine-tune the parameters of model calculations and as fingerprint properties of certain amino acids. In addition, we analyzed the low-temperature heat capacity of both the compounds and detected strong excess contributions compared to the canonical Debye behavior of crystalline solids, indicating soft excitations and a strongly enhanced phonon-density of states at low frequencies.

Die thermische Ausdehnung spielt eine Schlüsselrolle beim Verständnis des Schmelzens kristalliner Materialien. Die mikroskopischen Vorgänge beim Übergang von Gläsern in die flüssige Phase, und umgekehrt, sind allerdings noch weitgehend unverstanden. Durch die Analyse der thermischen Ausdehnungskoeffizienten und Glasübergangstemperaturen von mehr als 200 glasbildenden Materialien hat unser Forschungsteam nun unerwartet universelle Korrelationen dieser Größen aufgedeckt – ein Hinweis auf die wichtige Rolle kooperativer Teilchenbewegungen beim Glasübergang.

Using a combination of resistance fluctuation (noise) and dielectric spectroscopy we investigate the nature of relaxor-type electronic ferroelectricity in the organic conductor $\kappa$-(BETS)$_2$Mn[N(CN)$_2$]$_3$, a system representative for a wider class of materials, where strong correlations of electrons on a lattice of dimerized molecules results in an insulating ground state. The two complementary spectroscopies reveal a distinct low-frequency dynamics. By dielectric spectroscopy we detect an intrinsic relaxation that is typical for relaxor ferroelectrics below the metal-to-insulator transition at $T_{\rm{MI}}\sim 25\,$K. Resistance noise spectroscopy reveals fluctuating two-level processes above $T_{\rm MI}$ which strongly couple to the applied electric field, a signature of fluctuating polar nanoregions (PNR), i.e. clusters of quantum electric dipoles fluctuating collectively. The PNR preform above the metal insulator transition. Upon cooling through $T_{\rm MI}$, a drastic increase of the low-frequency $1/f$-type fluctuations and slowing down of the charge carrier dynamics is accompanied by the onset of strong non-equilibrium dynamics indicating a glassy transition of interacting dipolar clusters, the scaling properties of which are consistent with a droplet model. The freezing of nano-scale polar clusters and non-equilibrium dynamics is suggested to be a common feature of organic relaxor-type electronic ferroelectrics and needs to be considered in theoretical models describing these materials.

By using dielectric spectroscopy in a broad range of temperatures and frequencies, we have investigated dipolar relaxations, the dc conductivity, and the possible occurrence of polar order in AgCN. The conductivity contributions dominate the dielectric response at elevated temperatures and low frequencies, most likely arising from the mobility of the small silver ions. In addition, we observe the dipolar relaxation dynamics of the dumbbell-shaped CN- ions, whose temperature dependence follows the Arrhenius behavior with a hindering barrier of 0.59 eV (57 kJ/mol). It correlates well with a systematic development of the relaxation dynamics with the cation radius, previously observed in various alkali cyanides. By comparison with the latter, we conclude that AgCN does not exhibit a plastic high-temperature phase with free rotation of the cyanide ions. Instead, our results indicate that a phase with quadrupolar order, revealing dipolar head-to-tail disorder of the CN- ions, exists at elevated temperatures up to the decomposition temperature, which crosses over to long-range polar order of the CN dipole moments below about 475 K. Dipole ordering was also reported for NaCN and KCN, and a comparison with these systems suggests a critical relaxation rate of 105-107 Hz, marking the onset of dipolar order in the cyanides. The detected relaxation dynamics in this order-disorder type polar state points to glasslike freezing below about 195 K of a fraction of non-ordered CN dipoles.

By modifying organic ligands of metal-organic framework with dipolar units, they turn suitable for various applications, e.g., in the field of sensor systems or switching of gas permeation. Dipolar linkers in the organic ligand are capable to rotate in certain temperature and frequency ranges. The copper-bearing paddlewheel shaped metal-organic frameworks ZJNU-40 and JLU-Liu30 possess such a polarizable dipole moment due to their benzothiadiazole moiety in the organic ligands. Here, we investigate the molecular rotor behavior of benzothiadiazole units of the two carboxylate-based MOFs by dielectric spectroscopy and computational simulation. Our dielectric results provide clear evidence for significant reorientational relaxation dynamics of these rotors, revealing various characteristics of glasslike freezing upon cooling. The calculated rotational energy barriers are consistent with experimentally determined barriers for single-dipole dynamics. Moreover, for JLU-Liu30 we find hints at antipolar ordering below about 300 K.