Charge and momentum transfer in supercooled melts: Why should their relaxation times differ?

The steady state values of the viscosity and the intrinsic ionic-conductivity of quenched melts are computed, in terms of independently measurable quantities. The frequency dependence of the ac dielectric response is estimated. The discrepancy between the corresponding characteristic relaxation times is only apparent; it does not imply distinct mechanisms, but stems from the intrinsic barrier distribution for $\alpha$-relaxation in supercooled fluids and glasses. This type of intrinsic ``decoupling'' is argued not to exceed four orders in magnitude, for known glassformers. We explain the origin of the discrepancy between the stretching exponent $\beta$, as extracted from $\epsilon(\omega)$ and the dielectric modulus data. The actual width of the barrier distribution always grows with lowering the temperature. The contrary is an artifact of the large contribution of the dc-conductivity component to the modulus data. The methodology allows one to single out other contributions to the conductivity, as in ``superionic'' liquids or when charge carriers are delocalized, implying that in those systems, charge transfer does not require structural reconfiguration.Comment: submitted to J Chem Phy

Dielectric spectroscopy on aging glasses

In the present work, we provide further evidence for the applicability of a modified stretched-exponential behavior, proposed recently for the description of aging-time dependent data below the glass temperature [P. Lunkenheimer et al., Phys. Rev. Lett. 95 (2005) 055702]. We analyze time-dependent dielectric loss data in a variety of aging glasses, including new data on Salol and propylene carbonate, using a conventional stretched exponential and the newly proposed approach. Also the scaling of aging data obtained at different measuring frequencies, which was predicted on the basis of the new approach, is checked for its validity.Comment: 6 pages, 5 figures, submitted to proceedings of 5th IDMRCS, Lille, 200

Structural influence on atomic hopping and electronic states of Pd-based bulk metallic glasses

Atomic motion and electronic structures of Pd–Ni–Cu–P bulk metallic glasses were investigated using 31P nuclear magnetic resonance. The hopping rate of P atoms was determined by the stimulated echo technique. Significant hopping was observed in all alloys well below the glass transition temperature. Increasing the Cu content to above 25 at. % increases P hopping significantly, consistent with the previous finding that the openness of the structure increases with Cu content. In contrast, P hopping is not influenced by changes of local electronic states at P sites, induced by the substitution of Ni by Cu

Time-temperature superposition in viscous liquids

Dielectric relaxation measurements on supercooled triphenyl phosphite show that at low temperatures time-temperature superposition (TTS) is accurately obeyed for the primary (alpha) relaxation process. Measurements on 6 other molecular liquids close to the calorimetric glass transition indicate that TTS is linked to an $\omega^{-1/2}$ high-frequency decay of the alpha loss, while the loss peak width is nonuniversal.Comment: 4 page

Crossover behavior and multi-step relaxation in a schematic model of the cut-off glass transition

We study a schematic mode-coupling model in which the ideal glass transition is cut off by a decay of the quadratic coupling constant in the memory function. (Such a decay, on a time scale tau_I, has been suggested as the likely consequence of activated processes.) If this decay is complete, so that only a linear coupling remains at late times, then the alpha relaxation shows a temporal crossover from a relaxation typical of the unmodified schematic model to a final strongly slower-than-exponential relaxation. This crossover, which differs somewhat in form from previous schematic models of the cut-off glass transition, resembles light-scattering experiments on colloidal systems, and can exhibit a `slower-than-alpha' relaxation feature hinted at there. We also consider what happens when a similar but incomplete decay occurs, so that a significant level of quadratic coupling remains for t>>tau_I. In this case the correlator acquires a third, weaker relaxation mode at intermediate times. This empirically resembles the beta process seen in many molecular glass formers. It disappears when the initial as well as the final quadratic coupling lies on the liquid side of the glass transition, but remains present even when the final coupling is only just inside the liquid (so that the alpha relaxation time is finite, but too long to measure). Our results are suggestive of how, in a cut-off glass, the underlying `ideal' glass transition predicted by mode-coupling theory can remain detectable through qualitative features in dynamics.Comment: 14 pages revtex inc 10 figs; submitted to pr

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

Resource Competition on Integral Polymatroids

We study competitive resource allocation problems in which players distribute their demands integrally on a set of resources subject to player-specific submodular capacity constraints. Each player has to pay for each unit of demand a cost that is a nondecreasing and convex function of the total allocation of that resource. This general model of resource allocation generalizes both singleton congestion games with integer-splittable demands and matroid congestion games with player-specific costs. As our main result, we show that in such general resource allocation problems a pure Nash equilibrium is guaranteed to exist by giving a pseudo-polynomial algorithm computing a pure Nash equilibrium.Comment: 17 page

Energy landscape - a key concept for the dynamics of glasses and liquids

There is a growing belief that the mode coupling theory is the proper microscopic theory for the dynamics of the undercooled liquid above a critical temperature T_c. In addition, there is some evidence that the system leaves the saddlepoints of the energy landscape to settle in the valleys at this critical temperature. Finally, there is a microscopic theory for the entropy at the calorimetric glass transition T_g by Mezard and Parisi, which allows to calculate the Kauzmann temperature from the atomic pair potentials. The dynamics of the frozen glass phase is at present limited to phenomenological models. In the spirit of the energy landscape concept, one considers an ensemble of independent asymmetric double-well potentials with a wide distribution of barrier heights and asymmetries (ADWP or Gilroy-Phillips model). The model gives an excellent description of the relaxation of glasses up to about T_g/4. Above this temperature, the interaction between different relaxation centers begins to play a role. One can show that the interaction reduces the number of relaxation centers needed to bring the shear modulus down to zero by a factor of three.Comment: Contribution to the III Workshop on Nonequilibrium Phenomena in Supercooled Fluids, Glasses and Amorphous Materials, 22-27 September 2002, Pisa; 14 pages, 3 figures; Version 3 takes criticque at Pisa into account; final version 4 will be published in J.Phys.: Condens.Matte

Scaling behavior in the β\beta-relaxation regime of a supercooled Lennard-Jones mixture

We report the results of a molecular dynamics simulation of a supercooled binary Lennard-Jones mixture. By plotting the self intermediate scattering functions vs. rescaled time, we find a master curve in the $\beta$-relaxation regime. This master curve can be fitted well by a power-law for almost three decades in rescaled time and the scaling time, or relaxation time, has a power-law dependence on temperature. Thus the predictions of mode-coupling-theory on the existence of a von Schweidler law are found to hold for this system; moreover, the exponents in these two power-laws are very close to satisfying the exponent relationship predicted by the mode-coupling-theory. At low temperatures, the diffusion constants also show a power-law behavior with the same critical temperature. However, the exponent for diffusion differs from that of the relaxation time, a result that is in disagreement with the theory.Comment: 8 pages, RevTex, four postscript figures available on request, MZ-Physics-10

Efficiency of scalar-parameterized mechanisms

We consider the problem of allocating a fixed amount of an infinitely divisible resource among multiple competing, fully rational users. We study the efficiency guarantees that are possible when we restrict to mechanisms that satisfy certain scalability constraints motivated by large scale communication networks; in particular, we restrict attention to mechanisms where users are restricted to one-dimensional strategy spaces. We first study the efficiency guarantees possible when the mechanism is not allowed to price differen- tiate. We study the worst-case efficiency loss (ratio of the utility associated with a Nash equilibrium to the maximum possible utility), and show that the proportional allocation mechanism of Kelly (1997) minimizes the efficiency loss when users are price anticipating. We then turn our attention to mechanisms where price differentiation is permitted; using an adaptation of the Vickrey-Clarke-Groves class of mechanisms, we con- struct a class of mechanisms with one-dimensional strategy spaces where Nash equilibria are fully efficient. These mechanisms are shown to be fully efficient even in general convex environments, under reasonable assumptions. Our results highlight a fundamental insight in mechanism design: when the pricing flexibility available to the mechanism designer is limited, restricting the strategic flexibility of bidders may actually improve the efficiency guarantee.National Science FoundationArmy Research OfficeDARPA - Next Generation Internet InitiativeNational Science Foundation Graduate Research Fellowshi