Dynamic Monte Carlo Simulations of Anisotropic Colloids

We put forward a simple procedure for extracting dynamical information from Monte Carlo simulations, by appropriate matching of the short-time diffusion tensor with its infinite-dilution limit counterpart, which is supposed to be known. This approach --discarding hydrodynamics interactions-- first allows us to improve the efficiency of previous Dynamic Monte Carlo algorithms for spherical Brownian particles. In a second step, we address the case of anisotropic colloids with orientational degrees of freedom. As an illustration, we present a detailed study of the dynamics of thin platelets, with emphasis on long-time diffusion and orientational correlations.Comment: 12 pages, 9 figure

Speckle visibility spectroscopy and variable granular fluidization

We introduce a dynamic light scattering technique capable of resolving motion that changes systematically, and rapidly, with time. It is based on the visibility of a speckle pattern for a given exposure duration. Applying this to a vibrated layer of glass beads, we measure the granular temperature and its variation with phase in the oscillation cycle. We observe several transitions involving jammed states, where the grains are at rest during some portion of the cycle. We also observe a two-step decay of the temperature on approach to jamming.Comment: 4 pages, 4 figures, experimen

Dynamic correlations in stochastic rotation dynamics

The dynamic structure factor, vorticity and entropy density dynamic correlation functions are measured for Stochastic Rotation Dynamics (SRD), a particle based algorithm for fluctuating fluids. This allows us to obtain unbiased values for the longitudinal transport coefficients such as thermal diffusivity and bulk viscosity. The results are in good agreement with earlier numerical and theoretical results, and it is shown for the first time that the bulk viscosity is indeed zero for this algorithm. In addition, corrections to the self-diffusion coefficient and shear viscosity arising from the breakdown of the molecular chaos approximation at small mean free paths are analyzed. In addition to deriving the form of the leading correlation corrections to these transport coefficients, the probabilities that two and three particles remain collision partners for consecutive time steps are derived analytically in the limit of small mean free path. The results of this paper verify that we have an excellent understanding of the SRD algorithm at the kinetic level and that analytic expressions for the transport coefficients derived elsewhere do indeed provide a very accurate description of the SRD fluid.Comment: 33 pages including 16 figure

Unexpected Effect of Internal Degrees of Freedom on Transverse Phonons in Supercooled Liquids

We show experimentally that in a supercooled liquid composed of molecules with internal degrees of freedom the internal modes contribute to the frequency dependent shear viscosity and damping of transverse phonons, which results in an additional broadening of the transverse Brillouin lines. Earlier, only the effect of internal modes on the frequency dependent bulk viscosity and damping of longitudinal phonons was observed and explained theoretically in the limit of weak coupling of internal degrees of freedom to translational motion. A new theory is needed to describe this new effect. We also demonstrate, that the contributions of structural relaxation and internal processes to the width of the Brillouin lines can be separated by measurements under high pressure

Resolving long-range spatial correlations in jammed colloidal systems using photon correlation imaging

We introduce a new dynamic light scattering method, termed photon correlation imaging, which enables us to resolve the dynamics of soft matter in space and time. We demonstrate photon correlation imaging by investigating the slow dynamics of a quasi two-dimensional coarsening foam made of highly packed, deformable bubbles and a rigid gel network formed by dilute, attractive colloidal particles. We find the dynamics of both systems to be determined by intermittent rearrangement events. For the foam, the rearrangements extend over a few bubbles, but a small dynamical correlation is observed up to macroscopic length scales. For the gel, dynamical correlations extend up to the system size. These results indicate that dynamical correlations can be extremely long-ranged in jammed systems and point to the key role of mechanical properties in determining their nature.Comment: Published version (Phys. Rev. Lett. 102, 085702 (2009)) The Dynamical Activity Mapsprovided as Supplementary Online Material are also available on http://w3.lcvn.univ-montp2.fr/~lucacip/dam/movies.ht

Quantized time correlation function approach to non-adiabatic decay rates in condensed phase: Application to solvated electrons in water and methanol

A new, alternative form of the golden rule formula defining the non-adiabatic transition rate between two quantum states in condensed phase is presented. The formula involves the quantum time correlation function of the energy gap, of the non-adiabatic coupling, and their cross terms. Those quantities can be inferred from their classical counterparts, determined via MD simulations. The formalism is applied to the problem of the non-adiabatic relaxation of an equilibrated p-electron in water and methanol. We find that, in both solvent, the relaxation is induced by the coupling to the vibrational modes and the quantum effects modify the rate by a factor of 2-10 depending on the quantization procedure applied. The resulting p-state lifetime for a hypothetical equilibrium excited state appears extremely short, in the sub-100 fs regime. Although this result is in contrast with all previous theoretical predictions, we also illustrate that the lifetimes computed here are very sensitive to the simulated electronic quantum gap and to the strongly correlated non-adiabatic coupling

On the origin of the λ\lambda-transition in liquid Sulphur

Developing a novel experimental technique, we applied photon correlation spectroscopy using infrared radiation in liquid Sulphur around $T_\lambda$, i.e. in the temperature range where an abrupt increase in viscosity by four orders of magnitude is observed upon heating within few degrees. This allowed us - overcoming photo-induced and absorption effects at visible wavelengths - to reveal a chain relaxation process with characteristic time in the ms range. These results do rehabilitate the validity of the Maxwell relation in Sulphur from an apparent failure, allowing rationalizing the mechanical and thermodynamic behavior of this system within a viscoelastic scenario.Comment: 5 pages, 4 eps figures, accepted in Phys. Rev. Let

Length scale dependence of dynamical heterogeneity in a colloidal fractal gel

We use time-resolved dynamic light scattering to investigate the slow dynamics of a colloidal gel. The final decay of the average intensity autocorrelation function is well described by $g\_2(q,\tau)-1 \sim \exp[-(\tau/\tau\_\mathrm{f})^p]$, with $\tau\_\mathrm{f} \sim q^{-1}$ and $p$ decreasing from 1.5 to 1 with increasing $q$. We show that the dynamics is not due to a continuous ballistic process, as proposed in previous works, but rather to rare, intermittent rearrangements. We quantify the dynamical fluctuations resulting from intermittency by means of the variance $\chi(\tau,q)$ of the instantaneous autocorrelation function, the analogous of the dynamical susceptibility $\chi\_4$ studied in glass formers. The amplitude of $\chi$ is found to grow linearly with $q$. We propose a simple --yet general-- model of intermittent dynamics that accounts for the $q$ dependence of both the average correlation functions and $\chi$.Comment: Revised and improved, to appear in Europhys. Let

Liquid Transport Due to Light Scattering

Using experiments and theory, we show that light scattering by inhomogeneities in the index of refraction of a fluid can drive a large-scale flow. The experiment uses a near-critical, phase-separated liquid, which experiences large fluctuations in its index of refraction. A laser beam traversing the liquid produces a large-scale deformation of the interface and can cause a liquid jet to form. We demonstrate that the deformation is produced by a scattering-induced flow by obtaining good agreements between the measured deformations and those calculated assuming this mechanism.Comment: 4 pages, 5 figures, submitted to Physical Review Letters v2: Edited based on comments from referee

Reconstruction of thermally-symmetrized quantum autocorrelation functions from imaginary-time data

In this paper, I propose a technique for recovering quantum dynamical information from imaginary-time data via the resolution of a one-dimensional Hamburger moment problem. It is shown that the quantum autocorrelation functions are uniquely determined by and can be reconstructed from their sequence of derivatives at origin. A general class of reconstruction algorithms is then identified, according to Theorem 3. The technique is advocated as especially effective for a certain class of quantum problems in continuum space, for which only a few moments are necessary. For such problems, it is argued that the derivatives at origin can be evaluated by Monte Carlo simulations via estimators of finite variances in the limit of an infinite number of path variables. Finally, a maximum entropy inversion algorithm for the Hamburger moment problem is utilized to compute the quantum rate of reaction for a one-dimensional symmetric Eckart barrier.Comment: 15 pages, no figures, to appear in Phys. Rev.