Connection between slow and fast dynamics of molecular liquids around the glass transition

The mean-square displacement (MSD) was measured by neutron scattering at various temperatures and pressures for a number of molecular glass-forming liquids. The MSD is invariant along the glass-transition line at the pressure studied, thus establishing an ``intrinsic'' Lindemann criterion for any given liquid. A one-to-one connection between the MSD's temperature dependence and the liquid's fragility is found when the MSD is evaluated on a time scale of approximately 4 nanoseconds, but does not hold when the MSD is evaluated at shorter times. The findings are discussed in terms of the elastic model and the role of relaxations, and the correlations between slow and fast dynamics are addressed.Comment: accepted by Phys Rev E (2010

On the correlation between fragility and stretching in glassforming liquids

We study the pressure and temperature dependences of the dielectric relaxation of two molecular glassforming liquids, dibutyl phtalate and m-toluidine. We focus on two characteristics of the slowing down of relaxation, the fragility associated with the temperature dependence and the stretching characterizing the relaxation function. We combine our data with data from the literature to revisit the proposed correlation between these two quantities. We do this in light of constraints that we suggest to put on the search for empirical correlations among properties of glassformers. In particular, argue that a meaningful correlation is to be looked for between stretching and isochoric fragility, as both seem to be constant under isochronic conditions and thereby reflect the intrinsic effect of temperature

The consequence of excess configurational entropy on fragility: the case of a polymer/oligomer blend

By taking advantage of the molecular weight dependence of the glass transition of polymers and their ability to form perfectly miscible blends, we propose a way to modify the fragility of a system, from fragile to strong, keeping the same glass properties, i.e. vibrational density of states, mean-square displacement and local structure. Both slow and fast dynamics are investigated by calorimetry and neutron scattering in an athermal polystyrene/oligomer blend, and compared to those of a pure 17-mer polystyrene considered to be a reference, of same Tg. Whereas the blend and the pure 17-mer have the same heat capacity in the glass and in the liquid, their fragilities differ strongly. This difference in fragility is related to an extra configurational entropy created by the mixing process and acting at a scale much larger than the interchain distance, without affecting the fast dynamics and the structure of the glass

Colloids in light fields: particle dynamics in random and periodic energy landscapes

The dynamics of colloidal particles in potential energy landscapes have mainly been investigated theoretically. In contrast, here we discuss the experimental realization of potential energy landscapes with the help of light fields and the observation of the particle dynamics by video microscopy. The experimentally observed dynamics in periodic and random potentials are compared to simulation and theoretical results in terms of, e.g. the mean-squared displacement, the time-dependent diffusion coefficient or the non-Gaussian parameter. The dynamics are initially diffusive followed by intermediate subdiffusive behaviour which again becomes diffusive at long times. How pronounced and extended the different regimes are, depends on the specific conditions, in particular the shape of the potential as well as its roughness or amplitude but also the particle concentration. Here we focus on dilute systems, but the dynamics of interacting systems in external potentials, and thus the interplay between particle-particle and particle-potential interactions, is also mentioned briefly. Furthermore, the observed dynamics of dilute systems resemble the dynamics of concentrated systems close to their glass transition, with which it is compared. The effect of certain potential energy landscapes on the dynamics of individual particles appears similar to the effect of interparticle interactions in the absence of an external potential

Dynamic heterogeneities in attractive colloids

We study the formation of a colloidal gel by means of Molecular Dynamics simulations of a model for colloidal suspensions. A slowing down with gel-like features is observed at low temperatures and low volume fractions, due to the formation of persistent structures. We show that at low volume fraction the dynamic susceptibility, which describes dynamic heterogeneities, exhibits a large plateau, dominated by clusters of long living bonds. At higher volume fraction, where the effect of the crowding of the particles starts to be present, it crosses over towards a regime characterized by a peak. We introduce a suitable mean cluster size of clusters of monomers connected by "persistent" bonds which well describes the dynamic susceptibility.Comment: 4 pages, 4 figure

Non-monotonic temperature evolution of dynamic correlations in glass-forming liquids

The viscosity of glass-forming liquids increases by many orders of magnitude if their temperature is lowered by a mere factor of 2-3 [1,2]. Recent studies suggest that this widespread phenomenon is accompanied by spatially heterogeneous dynamics [3,4], and a growing dynamic correlation length quantifying the extent of correlated particle motion [5-7]. Here we use a novel numerical method to detect and quantify spatial correlations which reveal a surprising non-monotonic temperature evolution of spatial dynamical correlations, accompanied by a second length scale that grows monotonically and has a very different nature. Our results directly unveil a dramatic qualitative change in atomic motions near the mode-coupling crossover temperature [8] which involves no fitting or indirect theoretical interpretation. Our results impose severe new constraints on the theoretical description of the glass transition, and open several research perspectives, in particular for experiments, to confirm and quantify our observations in real materials.Comment: 7 page

Temperature dependence of three point correlation functions of viscous liquids the case of glycerol

What causes the dramatic slowing down of amp; 64258;ow and relaxation that leads to glass formation in liquids as temperature decreases is hardly understood so far and sub ject of intensive research work. It is tempting to ascribe the strong temperature dependence of the dynamics, irrespective of molecular details, to a collective or cooperative behaviour characterized by a length scale that grows as one approaches the glass transition. To access this length experimentally, we use the recently introduced three point dynamic susceptibility, from which can be extracted a number of molecules dynamically correlated during the structural relaxation, Ncorr. The three point functions are related to the sensitivity of the averaged two time dynamics to external control parameters, such as temperature and density. We studied Ncorr values in an important temperature range for a large number of liquids, and found that it systematically grows when approaching the glass transition. We specially emphasize here the case of glycerol for which we combined dielectric and neutron spin echo spectroscopy to cover more than 16 decades in relaxation tim