Asymptotic laws for tagged-particle motion in glassy systems

Within the mode-coupling theory for structural relaxation in simple systems the asymptotic laws and their leading-asymptotic correction formulas are derived for the motion of a tagged particle near a glass-transition singularity. These analytic results are compared with numerical ones of the equations of motion evaluated for a tagged hard sphere moving in a hard-sphere system. It is found that the long-time part of the two-step relaxation process for the mean-squared displacement can be characterized by the $\alpha$-relaxation-scaling law and von Schweidler's power-law decay while the critical-decay regime is dominated by the corrections to the leading power-law behavior. For parameters of interest for the interpretations of experimental data, the corrections to the leading asymptotic laws for the non-Gaussian parameter are found to be so large that the leading asymptotic results are altered qualitatively by the corrections. Results for the non-Gaussian parameter are shown to follow qualitatively the findings reported in the molecular-dynamics-simulations work by Kob and Andersen [Phys. Rev. E 51, 4626 (1995)]

A quantitative test of the mode-coupling theory of the ideal glass transition for a binary Lennard-Jones system

Using a molecular dynamics computer simulation we determine the temperature dependence of the partial structure factors for a binary Lennard-Jones system. These structure factors are used as input data to solve numerically the wave-vector dependent mode-coupling equations in the long time limit. Using the so determined solutions, we compare the predictions of mode-coupling theory (MCT) with the results of a previously done molecular dynamics computer simulation [Phys. Rev. E 51, 4626 (1995), ibid. 52, 4134 (1995)]. From this comparison we conclude that MCT gives a fair estimate of the critical coupling constant, a good estimate of the exponent parameter, predicts the wave-vector dependence of the various nonergodicity parameters very well, except for very large wave-vectors, and gives also a very good description of the space dependence of the various critical amplitudes. In an attempt to correct for some of the remaining discrepancies between the theory and the results of the simulation, we investigate two small (ad hoc) modifications of the theory. We find that one modification gives a worse agreement between theory and simulation, whereas the second one leads to an improved agreement.Comment: Figures available from W. Ko

Differential Cyclic Voltammetry - a Novel Technique for Selective and Simultaneous Detection using Redox Cycling Based Sensors

Redox cycling (RC) is an effect that is used to amplify electrochemical signals. However, traditional techniques such as cyclic voltammetry (CV) do not provide clear insight for a mixture of multiple redox couples while RC is applied. Thus, we have developed a new measurement technique which delivers electrochemical spectra of all reversible redox couples present based on concentrations and standard potentials. This technique has been named differential cyclic voltammetry (DCV). We have fabricated micrometer-sized interdigitated electrode (IDE) sensors to conduct DCV measurements in mixtures of 1mM catechol and 4mM [Ru(NH3)6]Cl3. To simulate the electrochemical behavior of these sensors we have also developed a finite element model (FEM) in Comsol®. The\ud experimental data corresponds to the calculated spectra obtained from simulations. Additionally, the measured spectra can be used to easily derive standard potentials and concentrations simultaneously and selectively.\u

Higher order glass-transition singularities in colloidal systems with attractive interactions

The transition from a liquid to a glass in colloidal suspensions of particles interacting through a hard core plus an attractive square-well potential is studied within the mode-coupling-theory framework. When the width of the attractive potential is much shorter than the hard-core diameter, a reentrant behavior of the liquid-glass line, and a glass-glass-transition line are found in the temperature-density plane of the model. For small well-width values, the glass-glass-transition line terminates in a third order bifurcation point, i.e. in a A_3 (cusp) singularity. On increasing the square-well width, the glass-glass line disappears, giving rise to a fourth order A_4 (swallow-tail) singularity at a critical well width. Close to the A_3 and A_4 singularities the decay of the density correlators shows stretching of huge dynamical windows, in particular logarithmic time dependence.Comment: 19 pages, 12 figures, Phys. Rev. E, in prin

Aspects of the dynamics of colloidal suspensions: Further results of the mode-coupling theory of structural relaxation

Results of the idealized mode-coupling theory for the structural relaxation in suspensions of hard-sphere colloidal particles are presented and discussed with regard to recent light scattering experiments. The structural relaxation becomes non-diffusive for long times, contrary to the expectation based on the de Gennes narrowing concept. A semi-quantitative connection of the wave vector dependences of the relaxation times and amplitudes of the final $\alpha$-relaxation explains the approximate scaling observed by Segr{\`e} and Pusey [Phys. Rev. Lett. {\bf 77}, 771 (1996)]. Asymptotic expansions lead to a qualitative understanding of density dependences in generalized Stokes-Einstein relations. This relation is also generalized to non-zero frequencies thereby yielding support for a reasoning by Mason and Weitz [Phys. Rev. Lett {\bf 74}, 1250 (1995)]. The dynamics transient to the structural relaxation is discussed with models incorporating short-time diffusion and hydrodynamic interactions for short times.Comment: 11 pages, 9 figures; to be published in Phys. Rev.

Direct visualization of aging in colloidal glasses

We use confocal microscopy to directly visualize the dynamics of aging colloidal glasses. We prepare a colloidal suspension at high density, a simple model system which shares many properties with other glasses, and initiate experiments by stirring the sample. We follow the motion of several thousand colloidal particles after the stirring and observe that their motion significantly slows as the sample ages. The aging is both spatially and temporally heterogeneous. Furthermore, while the characteristic relaxation time scale grows with the age of the sample, nontrivial particle motions continue to occur on all time scales.Comment: submitted to proceedings for Liquid Matter Conference 200

Dynamics of hard-sphere suspension using Dynamic Light Scattering and X-Ray Photon Correlation Spectroscopy: dynamics and scaling of the Intermediate Scattering Function

Intermediate Scattering Functions (ISF's) are measured for colloidal hard sphere systems using both Dynamic Light Scattering (DLS) and X-ray Photon Correlation Spectroscopy (XPCS). We compare the techniques, and discuss the advantages and disadvantages of each. Both techniques agree in the overlapping range of scattering vectors. We investigate the scaling behaviour found by Segre and Pusey [1] but challenged by Lurio et al. [2]. We observe a scaling behaviour over several decades in time but not in the long time regime. Moreover, we do not observe long time diffusive regimes at scattering vectors away from the peak of the structure factor and so question the existence of a long time diffusion coefficients at these scattering vectors.Comment: 21 pages, 11 figure

How does the relaxation of a supercooled liquid depend on its microscopic dynamics?

Using molecular dynamics computer simulations we investigate how the relaxation dynamics of a simple supercooled liquid with Newtonian dynamics differs from the one with a stochastic dynamics. We find that, apart from the early beta-relaxation regime, the two dynamics give rise to the same relaxation behavior. The increase of the relaxation times of the system upon cooling, the details of the alpha-relaxation, as well as the wave vector dependence of the Edwards-Anderson-parameters are independent of the microscopic dynamics.Comment: 6 pages of Latex, 4 figure

Ageing dynamics of colloidal hard sphere glasses

We report results of dynamic light scattering measurements of the coherent intermediate scattering function (ISF) of glasses of hard spheres for several volume fractions and a range of scattering vectors around the primary maximum of the static structure factor. The ISF shows a clear crossover from an initial fast decay to a slower non-stationary decay. Ageing is quantified in several different ways. However, regardless of the method chosen, the perfect "aged" glass is approached in a power-law fashion. In particular, the coupling between the fast and slow decays, as measured by the degree of stretching of the ISF at the crossover, also decreases algebraically with waiting time. The non-stationarity of this coupling implies that even the fastest detectable processes are themselves non-stationary.Comment: 28 pages, including 3 tables and 17 figure