Avalanches and Dynamical Correlations in supercooled liquids

We identify the pattern of microscopic dynamical relaxation for a two dimensional glass forming liquid. On short timescales, bursts of irreversible particle motion, called cage jumps, aggregate into clusters. On larger time scales, clusters aggregate both spatially and temporally into avalanches. This propagation of mobility, or dynamic facilitation, takes place along the soft regions of the systems, which have been identified by computing isoconfigurational Debye-Waller maps. Our results characterize the way in which dynamical heterogeneity evolves in moderately supercooled liquids and reveal that it is astonishingly similar to the one found for dense glassy granular media.Comment: 4 pages, 3 figure

Molecular shape and the energetics of chemisorption: From simple to complex energy landscapes

We enumerate all local minima of the energy landscape for model rigid adsorbates characterized by three or four equivalent binding sites (e.g., thiol groups) on a close-packed (111) surface of a face-centered-cubic crystal. We show that the number of energy minima increases linearly with molecular size with a rate of increase that depends on the degree of registry between the molecule shape and the surface structure. The sparseness of energy minima and the large variations in the center-of-mass positions of these minima vs molecular size for molecules that are incommensurate with the surface suggests a strong coupling in these molecules between surface mobility and shape or size fluctuations resulting from molecular vibrations. We also find that the variation in the binding energy with respect to molecular size decreases more rapidly with molecular size for molecules with a higher degree of registry with the surface. This indicates that surface adsorption should be better able to distinguish molecules by size if the molecules are incommensurate with the surface.David M. Huang and Peter Harrowel

Facilitated spin models: recent and new results

Facilitated or kinetically constrained spin models (KCSM) are a class of interacting particle systems reversible w.r.t. to a simple product measure. Each dynamical variable (spin) is re-sampled from its equilibrium distribution only if the surrounding configuration fulfills a simple local constraint which \emph{does not involve} the chosen variable itself. Such simple models are quite popular in the glass community since they display some of the peculiar features of glassy dynamics, in particular they can undergo a dynamical arrest reminiscent of the liquid/glass transitiom. Due to the fact that the jumps rates of the Markov process can be zero, the whole analysis of the long time behavior becomes quite delicate and, until recently, KCSM have escaped a rigorous analysis with the notable exception of the East model. In these notes we will mainly review several recent mathematical results which, besides being applicable to a wide class of KCSM, have contributed to settle some debated questions arising in numerical simulations made by physicists. We will also provide some interesting new extensions. In particular we will show how to deal with interacting models reversible w.r.t. to a high temperature Gibbs measure and we will provide a detailed analysis of the so called one spin facilitated model on a general connected graph.Comment: 30 pages, 3 figure

Phase field modeling of electrochemistry I: Equilibrium

A diffuse interface (phase field) model for an electrochemical system is developed. We describe the minimal set of components needed to model an electrochemical interface and present a variational derivation of the governing equations. With a simple set of assumptions: mass and volume constraints, Poisson's equation, ideal solution thermodynamics in the bulk, and a simple description of the competing energies in the interface, the model captures the charge separation associated with the equilibrium double layer at the electrochemical interface. The decay of the electrostatic potential in the electrolyte agrees with the classical Gouy-Chapman and Debye-H\"uckel theories. We calculate the surface energy, surface charge, and differential capacitance as functions of potential and find qualitative agreement between the model and existing theories and experiments. In particular, the differential capacitance curves exhibit complex shapes with multiple extrema, as exhibited in many electrochemical systems.Comment: v3: To be published in Phys. Rev. E v2: Added link to cond-mat/0308179 in References 13 pages, 6 figures in 15 files, REVTeX 4, SIUnits.sty. Precedes cond-mat/030817

Critical fluctuations and breakdown of Stokes-Einstein relation in the Mode-Coupling Theory of glasses

We argue that the critical dynamical fluctuations predicted by the mode-coupling theory (MCT) of glasses provide a natural mechanism to explain the breakdown of the Stokes-Einstein relation. This breakdown, observed numerically and experimentally in a region where MCT should hold, is one of the major difficulty of the theory, for which we propose a natural resolution based on the recent interpretation of the MCT transition as a bona fide critical point with a diverging length scale. We also show that the upper critical dimension of MCT is d_c=8.Comment: Proceedings of the workshop on non-equilibrium phenomena in supercooled fluids, glasses and amorphous materials (17-22 September, 2006, Pisa

Jamming percolation and glassy dynamics

We present a detailed physical analysis of the dynamical glass-jamming transition which occurs for the so called Knight models recently introduced and analyzed in a joint work with D.S.Fisher \cite{letterTBF}. Furthermore, we review some of our previous works on Kinetically Constrained Models. The Knights models correspond to a new class of kinetically constrained models which provide the first example of finite dimensional models with an ideal glass-jamming transition. This is due to the underlying percolation transition of particles which are mutually blocked by the constraints. This jamming percolation has unconventional features: it is discontinuous (i.e. the percolating cluster is compact at the transition) and the typical size of the clusters diverges faster than any power law when $\rho\nearrow\rho_c$. These properties give rise for Knight models to an ergodicity breaking transition at $\rho_c$: at and above $\rho_{c}$ a finite fraction of the system is frozen. In turn, this finite jump in the density of frozen sites leads to a two step relaxation for dynamic correlations in the unjammed phase, analogous to that of glass forming liquids. Also, due to the faster than power law divergence of the dynamical correlation length, relaxation times diverge in a way similar to the Vogel-Fulcher law.Comment: Submitted to the special issue of Journal of Statistical Physics on Spin glasses and related topic

Making Space for Failure in Geographic Research

The idea that field research is an inherently “messy” process has become widely accepted by geographers in recent years. There has thus far been little acknowledgment, however, of the role that failure plays in doing human geography. In this article we push back against this, arguing that failure should be recognized as a central component of what it means to do qualitative geographical field research. This article seeks to use failure proactively and provocatively as a powerful resource to improve research practice and outcomes, reconsidering and giving voice to it as everyday, productive, and necessary to our continual development as researchers and academics. This article argues that there is much value to be found in failure if it is critically examined and shared, and—crucially—if there is a supportive space in which to exchange our experiences of failing in the field

Cooperative Behavior of Kinetically Constrained Lattice Gas Models of Glassy Dynamics

Kinetically constrained lattice models of glasses introduced by Kob and Andersen (KA) are analyzed. It is proved that only two behaviors are possible on hypercubic lattices: either ergodicity at all densities or trivial non-ergodicity, depending on the constraint parameter and the dimensionality. But in the ergodic cases, the dynamics is shown to be intrinsically cooperative at high densities giving rise to glassy dynamics as observed in simulations. The cooperativity is characterized by two length scales whose behavior controls finite-size effects: these are essential for interpreting simulations. In contrast to hypercubic lattices, on Bethe lattices KA models undergo a dynamical (jamming) phase transition at a critical density: this is characterized by diverging time and length scales and a discontinuous jump in the long-time limit of the density autocorrelation function. By analyzing generalized Bethe lattices (with loops) that interpolate between hypercubic lattices and standard Bethe lattices, the crossover between the dynamical transition that exists on these lattices and its absence in the hypercubic lattice limit is explored. Contact with earlier results are made via analysis of the related Fredrickson-Andersen models, followed by brief discussions of universality, of other approaches to glass transitions, and of some issues relevant for experiments.Comment: 59 page

The variety of ordering transitions in liquids characterized by a locally favoured structure

We present a new lattice model of liquids in which the energy of a configuration is determined by the local coordination environments rather than pairwise interactions. This model is used to explore how the accumulation of order on cooling depends on the geometry of the locally favoured structure. We find that, while high-symmetry local structures result in ordering that occurs predominantly via a thermodynamic freezing transition, liquids characterised by a low-symmetry local structure exhibit a significant increase in local order on cooling before crystallizing