Johari-Goldstein relaxation far below Tg: Experimental evidence for the Gardner transition in structural glasses?

Experimental evidence for the Gardner transition, theoretically predicted to arise deep in the glassy state of matter, is scarce. At this transition, the energy landscape sensed by the particles forming the glass is expected to become more complex. In the present work, we report the dielectric response of two typical glass formers with well-pronounced Johari-Goldstein beta relaxation following this response down to unprecedented low temperatures, far below the glass transition. As the Johari-Goldstein process is believed to arise from the local structure of the energy landscape, its investigation seems an ideal tool to seek evidence for the Gardner transition. Indeed, we find an unusual broadening of the beta relaxation below TG ~ 110 K for sorbitol and TG ~ 100 K for xylitol, in excess of the expected broadening arising from a distribution of energy barriers. Thus, these results provide hints at the presence of the Gardner transition in canonical structural glass formers.Comment: 6 pages, 3 figures + 2 pages, 3 figures in Supplemental Materia

Ionic conductivity and relaxation dynamics in plastic-crystals with nearly globular molecules

We have performed a dielectric investigation of the ionic charge transport and the relaxation dynamics in plastic-crystalline 1-cyano-adamantane (CNA) and in two mixtures of CNA with the related plastic crystals adamantane or 2-adamantanon. Ionic charge carriers were provided by adding 1% of Li salt. The molecules of these compounds have nearly globular shape and, thus, the so-called revolving-door mechanism assumed to promote ionic charge transport via molecular reorientations in other PC electrolytes, should not be active here. Indeed, a comparison of the dc resistivity and the reorientational alpha-relaxation times in the investigated PCs, reveals complete decoupling of both dynamics. Similar to other PCs, we find a significant mixing-induced enhancement of the ionic conductivity. Finally, these solid-state electrolytes reveal a second relaxation process, slower than the alpha-relaxation, which is related to ionic hopping. Due to the mentioned decoupling, it can be unequivocally detected and is not superimposed by the reorientational contributions as found for most other ionic conductors.Comment: 9 pages, 7 figure

Role of counterions in the adsorption and micellization behavior of 1:1 ionic surfactants at fluid interfaces─demonstrated by the standard amphiphile system of alkali perfluoro-n-octanoates

In our latest communication, we proved experimentally that the ionic surfactant’s surface excess is exclusively determined by the size of the hydrated counterion.[Lunkenheimer, Langmuir, 2017, 33, 10216−1022410.1021/acs.langmuir.7b00786]. However, at this stage of research, we were unable to decide whether this does only hold for the two or three lightest ions of lithium, sodium, and potassium, respectively. Alternatively, we could also consider the surface excess of the heavier hydrated alkali ions of potassium, rubidium, and cesium, having practically identical ion size, as being determined by the cross-sectional area of the related anionic extended chain residue. The latter assumption has represented state of art. Searching for reliable experimental results on the effect of the heavier counterions on the boundary layer, we have extended investigations to the amphiphiles’ solutions of concentrations above the critical concentration of micelle formation (cmc).We provided evidence that the super-micellar solutions’ equilibrium surface tension will remain constant provided the required conditions are followed. The related σcmccmccmc+ > Na+ > K+ > (NH4)+ > Rb+ > Cs+. Therefore, we have to extend our model of counterion effectiveness put forward in our previous communication. It represents a general principle of the counterion effect

Dielectric and conductivity relaxation in mixtures of glycerol with LiCl

We report a thorough dielectric characterization of the alpha relaxation of glass forming glycerol with varying additions of LiCl. Nine salt concentrations from 0.1 - 20 mol% are investigated in a frequency range of 20 Hz - 3 GHz and analyzed in the dielectric loss and modulus representation. Information on the dc conductivity, the dielectric relaxation time (from the loss) and the conductivity relaxation time (from the modulus) is provided. Overall, with increasing ion concentration, a transition from reorientationally to translationally dominated behavior is observed and the translational ion dynamics and the dipolar reorientational dynamics become successively coupled. This gives rise to the prospect that by adding ions to dipolar glass formers, dielectric spectroscopy may directly couple to the translational degrees of freedom determining the glass transition, even in frequency regimes where usually strong decoupling is observed.Comment: 8 pages, 7 figure

Relaxation dynamics and colossal magnetocapacitive effect in CdCr2S4

A thorough investigation of the relaxational dynamics in the recently discovered multiferroic CdCr2S4 showing a colossal magnetocapacitive effect has been performed. Broadband dielectric measurements without and with external magnetic fields up to 10 T provide clear evidence that the observed magnetocapacitive effect stems from enormous changes of the relaxation dynamics induced by the development of magnetic order.Comment: 4 pages, 4 figure

Debye relaxation and 250 K anomaly in glass forming monohydroxy alcohols

A previous dielectric, near-infrared (NIR), and nuclear magnetic resonance study on the hydrogen-bonded liquid 2-ethyl-1-hexanol [C. Gainaru et al., Phys. Rev. Lett. 107, 118304 (2011)] revealed anomalous behavior in various static quantities near 250 K. To check whether corresponding observations can be made for other monohydroxy alcohols as well, these experimental methods were applied to such substances with 5, 6, 7, 8, and 10 carbon atoms in their molecular backbone. All studied liquids exhibit a change of behavior near 250 K which is tentatively ascribed to effects of hydrogen bond cooperativity. By analyzing the NIR band intensities, a linear cluster size is derived that agrees with estimates from dielectric spectroscopy. All studied alcohols, except 4-methyl-3-heptanol, display a dominant Debye-like peak. Furthermore, neat 2-ethyl-1-butanol exhibits a well resolved structural relaxation in its dielectric loss spectrum which so far has only been observed for diluted monohydroxy alcohols.Comment: 39 pages including 12 figure

Orbital-Order Driven Ferroelectricity and Dipolar Relaxation Dynamics in Multiferroic GaMo4_4S8_8

We present the results of broadband dielectric spectroscopy of GaMo$_4$S$_8$, a lacunar spinel system that recently was shown to exhibit non-canonical, orbitally-driven ferroelectricity. Our study reveals complex relaxation dynamics of this multiferroic material, both above and below its Jahn-Teller transition at T$_{\textrm{JT}}=47$ K. Above T$_{\textrm{JT}}$, two types of coupled dipolar-orbital dynamics seem to compete: relaxations within cluster-like regions with short-range polar order like in relaxor ferroelectrics and critical fluctuations of only weakly interacting dipoles, the latter resembling the typical dynamics of order-disorder type ferroelectrics. Below the Jahn-Teller transition, the onset of orbital order drives the system into long-range ferroelectric order and dipolar dynamics within the ferroelectric domains is observed. The coupled dipolar and orbital relaxation behavior of GaMo$_4$S$_8$ above the Jahn-Teller transition markedly differs from that of the skyrmion host GaV$_4$S$_8$, which seems to be linked to differences in the structural distortions of the two systems on the unit-cell level.Comment: 6 pages, 3 figures + Supplemental Material (2 pages, 2 figures

Broadband dielectric spectroscopy on benzophenone: alpha relaxation, beta relaxation, and mode coupling theory

We have performed a detailed dielectric investigation of the relaxational dynamics of glass-forming benzophenone. Our measurements cover a broad frequency range of 0.1 Hz to 120 GHz and temperatures from far below the glass temperature well up into the region of the small-viscosity liquid. With respect to the alpha relaxation this material can be characterized as a typical molecular glass former with rather high fragility. A good agreement of the alpha relaxation behavior with the predictions of the mode coupling theory of the glass transition is stated. In addition, at temperatures below and in the vicinity of Tg we detect a well-pronounced beta relaxation of Johari-Goldstein type, which with increasing temperature develops into an excess wing. We compare our results to literature data from optical Kerr effect and depolarized light scattering experiments, where an excess-wing like feature was observed in the 1 - 100 GHz region. We address the question if the Cole-Cole peak, which was invoked to describe the optical Kerr effect data within the framework of the mode coupling theory, has any relation to the canonical beta relaxation detected by dielectric spectroscopy.Comment: 11 pages, 7 figures; revised version with new Fig. 5 and some smaller changes according to referees' demand

Plastic-crystalline solid-state electrolytes: Ionic conductivity and orientational dynamics in nitrile mixtures

Many plastic crystals, molecular solids with long-range, center-of-mass crystalline order but dynamic disorder of the molecular orientations, are known to exhibit exceptionally high ionic conductivity. This makes them promising candidates for applications as solid-state electrolytes, e.g., in batteries. Interestingly, it was found that the mixing of two different plastic-crystalline materials can considerably enhance the ionic dc conductivity, an important benchmark quantity for electrochemical applications. An example is the admixture of different nitriles to succinonitrile, the latter being one of the most prominent plastic-crystalline ionic conductors. However, until now only few such mixtures were studied. In the present work, we investigate succinonitrile mixed with malononitrile, adiponitrile, and pimelonitrile, to which 1 mol% of Li ions were added. Using differential scanning calorimetry and dielectric spectroscopy, we examine the phase behavior and the dipolar and ionic dynamics of these systems. We especially address the mixing-induced enhancement of the ionic conductivity and the coupling of the translational ionic mobility to the molecular reorientational dynamics, probably arising via a "revolving-door" mechanism.Comment: 9 pages, 7 figures; revised version as accepted for publication in J. Chem. Phy