Origin of non-exponential relaxation in a crystalline ionic conductor: a multi-dimensional 109Ag NMR study

The origin of the non-exponential relaxation of silver ions in the crystalline ion conductor Ag7P3S11 is analyzed by comparing appropriate two-time and three-time 109Ag NMR correlation functions. The non-exponentiality is due to a rate distribution, i.e., dynamic heterogeneities, rather than to an intrinsic non-exponentiality. Thus, the data give no evidence for the relevance of correlated back-and-forth jumps on the timescale of the silver relaxation.Comment: 4 pages, 3 figure

Glassy Phase Transition and Stability in Black Holes

Black hole thermodynamics, confined to the semi-classical regime, cannot address the thermodynamic stability of a black hole in flat space. Here we show that inclusion of correction beyond the semi-classical approximation makes a black hole thermodynamically stable. This stability is reached through a phase transition. By using Ehrenfest's scheme we further prove that this is a glassy phase transition with a Prigogine-Defay ratio close to 3. This value is well placed within the desired bound (2 to 5) for a glassy phase transition. Thus our analysis indicates a very close connection between the phase transition phenomena of a black hole and glass forming systems. Finally, we discuss the robustness of our results by considering different normalisations for the correction term.Comment: v3, minor changes over v2, references added, LaTeX-2e, 18 pages, 3 ps figures, to appear in Eour. Phys. Jour.

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

Complex lithium ion dynamics in simulated LiPO3 glass studied by means of multi-time correlation functions

Molecular dynamics simulations are performed to study the lithium jumps in LiPO3 glass. In particular, we calculate higher-order correlation functions that probe the positions of single lithium ions at several times. Three-time correlation functions show that the non-exponential relaxation of the lithium ions results from both correlated back-and-forth jumps and the existence of dynamical heterogeneities, i.e., the presence of a broad distribution of jump rates. A quantitative analysis yields that the contribution of the dynamical heterogeneities to the non-exponential depopulation of the lithium sites increases upon cooling. Further, correlated back-and-forth jumps between neighboring sites are observed for the fast ions of the distribution, but not for the slow ions and, hence, the back-jump probability depends on the dynamical state. Four-time correlation functions indicate that an exchange between fast and slow ions takes place on the timescale of the jumps themselves, i.e., the dynamical heterogeneities are short-lived. Hence, sites featuring fast and slow lithium dynamics, respectively, are intimately mixed. In addition, a backward correlation beyond the first neighbor shell for highly mobile ions and the presence of long-range dynamical heterogeneities suggest that fast ion migration occurs along preferential pathways in the glassy matrix. In the melt, we find no evidence for correlated back-and-forth motions and dynamical heterogeneities on the length scale of the next-neighbor distance.Comment: 12 pages, 13 figure

Dynamic mechanical thermal analysis of aqueous sugar solutions containing fructose, glucose, sucrose, maltose and lactose

The glass transition of glucose, fructose, lactose, maltose and sucrose solutions at maximum cryo-concentration was studied by Dynamic Mechanical Thermal Analysis (DMTA), using the disc bending technique. The glass transition temperatures were determined from the peaks in the loss modulus E′′, which corresponds theoretically to the resonance point (Maxwell model) for several input frequencies. The frequency dependence was well described by both an Arrhenius-type model and by the WLF (Williams, Landel and Ferry) equation, yielding glass transition temperatures for an average molecular vibration time of 100 s, which were similar to published midpoint temperatures determined by DSC scans. Some sugar mixtures were studied, yielding results that were well described by the Gordon–Taylor equation, using literature data. The frequency dependence of the viscoelastic ratio was also well approximated by an Arrhenius-type equation, with activation energies similar to those of the glass transition temperature and corresponded well to published values of the endset of glass transition

PRE-EXPONENTIAL TERM IN THE ARRHENIUS EQUATION FOR ELECTRICAL CONDUCTIVITY OF GLASS

Des résultats très précis pour la conductivité électrique pour une série de six verres de composition molaire 25(xNa2O + (1-x)K2O) - 5Al2O3 - 70SiO2 pour 0,95 ≤x≤ 1 ont été obtenus pour un assez grand intervalle de température (∼ 310°C). L'analyse de ces résultats suggère que le terme pré-exponentiel dans l'équation d'Arrhenius pour la conductivité ne dépend pas de la température.Very precise electrical conductivity data on a series of six glasses of molar composition 25(xNa2O + (1-x)K2O) - 5Al2O3 - 70SiO2 with 0.95 ≤ x ≤ 1 have been obtained over a large temperature range (∼ 310°C). Analysis of this data suggests that the pre-exponential term in the Arrhenius conductivity equation is temperature independent