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David Chandler

Publications and source records attributed to David Chandler.

69 records · Page 4Linked to original sources
arXiv2006

Lengthscale dependence of dynamic four-point susceptibilities in glass formers

Dynamical four-point susceptibilities measure the extent of spatial correlations in the dynamics of glass forming systems. We show how these susceptibilities depend on the length scales that necessarily form part of their definition. The behaviour of these susceptibilities is estimated by means of an analysis in terms of renewal processes within the context of dynamic facilitation. The analytic results are confirmed by numerical simulations of an atomistic model glass-former, and of two kinetically constrained models. Hence we argue that the scenario predicted by the dynamic facilitation approach is generic.

cond-mat.stat-mech↗
arXiv2005

Dynamic Pathways for Viral Capsid Assembly

We develop a class of models with which we simulate the assembly of particles into T1 capsid-like objects using Newtonian dynamics. By simulating assembly for many different values of system parameters, we vary the forces that drive assembly. For some ranges of parameters, assembly is facile, while for others, assembly is dynamically frustrated by kinetic traps corresponding to malformed or incompletely formed capsids. Our simulations sample many independent trajectories at various capsomer concentrations, allowing for statistically meaningful conclusions. Depending on subunit (i.e., capsomer) geometries, successful assembly proceeds by several mechanisms involving binding of intermediates of various sizes. We discuss the relationship between these mechanisms and experimental evaluations of capsid assembly processes.

q-bio.BM↗
arXiv2005

Dynamical Exchanges in Facilitated Models of Supercooled liquids

We investigate statistics of dynamical exchange events in coarse--grained models of supercooled liquids in spatial dimensions $d=1$, 2, and 3. The models, based upon the concept of dynamical facilitation, capture generic features of statistics of exchange times and persistence times. Here, distributions for both times are related, and calculated for cases of strong and fragile glass formers over a range of temperatures. Exchange time distributions are shown to be particularly sensitive to the model parameters and dimensions, and exhibit more structured and richer behavior than persistence time distributions. Mean exchange times are shown to be Arrhenius, regardless of models and spatial dimensions. Specifically, $ \sim c^{-2}$, with $c$ being the excitation concentration. Different dynamical exchange processes are identified and characterized from the underlying trajectories. We discuss experimental possibilities to test some of our theoretical findings.

cond-mat.stat-mech↗
arXiv2005

Space-time Thermodynamics of the Glass Transition

We consider the probability distribution for fluctuations in dynamical action and similar quantities related to dynamic heterogeneity. We argue that the so-called "glass transition" is a manifestation of low action tails in these distributions where the entropy of trajectory space is sub-extensive in time. These low action tails are a consequence of dynamic heterogeneity and an indication of phase coexistence in trajectory space. The glass transition, where the system falls out of equilibrium, is then an order-disorder phenomenon in space-time occurring at a temperature T_g which is a weak function of measurement time. We illustrate our perspective ideas with facilitated lattice models, and note how these ideas apply more generally.

cond-mat.stat-mech↗
arXiv2005

Heterogeneity and growing lengthscales in the dynamics of kinetically constrained lattice gases in two dimensions

We study dynamical heterogeneity and growing dynamical lengthscales in two kinetically constrained models, namely, the one- and two-vacancy assisted triangular lattice gases. One of the models is a strong glassformer and the other is a fragile glassformer. Both exhibit heterogeneous dynamics with broadly distributed timescales as seen in the distribution of persistence times. We show that the Stokes-Einstein relation is violated, to a greater degree in the fragile glassformer, and show how this violation is related to dynamic heterogeneity. We extract dynamical lengthscales from structure factors of mobile particles and show, quantitatively, the growth of this lengthscale as density increases. We comment on how the scaling of lengths and times in these models relates to that in facilitated spin models of glasses.

cond-mat.stat-mech↗
arXiv2005

Thermodynamics of Coarse Grained Models of Super-Cooled Liquids

In recent papers, we have argued that kinetically constrained coarse grained models can be applied to understand dynamic properties of glass forming materials, and we have used this approach in various applications that appear to validate this view. In one such paper [J.P. Garrahan and D. Chandler, Proc. Nat. Acad. Sci. USA 100, 9710 (2003)], among other things we argued that this approach also explains why the heat capacity discontinuity at the glass transition is generally larger for fragile materials than for strong materials. In the preceding article, Biroli, Bouchaud and Tarjus (BB&T) [cond-mat/0412024] have objected to our explanation on this point, arguing that the class of models we apply is inconsistent with both the absolute size and temperature dependence of the experimental specific heat. Their argument, however, neglects parameters associated with the coarse graining. Accounting for these parameters, we show here that our treatment of dynamics is not inconsistent with heat capacity discontinuities.

cond-mat.stat-mech↗
arXiv2005

Length scale for the onset of Fickian diffusion in supercooled liquids

The interplay between self-diffusion and excitation lines in space-time was recently studied in kinetically constrained models to explain the breakdown of the Stokes-Einstein law in supercooled liquids. Here, we further examine this interplay and its manifestation in incoherent scattering functions. In particular, we establish a dynamic length scale below which Fickian diffusion breaks down, as is observed in experiments and simulations. We describe the temperature dependence of this length scale in liquids of various fragilities, and provide analytical estimates for the van Hove and self-intermediate scattering functions.

cond-mat.stat-mech↗
arXiv2004

Dynamics of Nucleation in the Ising Model

Reactive pathways to nucleation in a three-dimensional Ising model at 60% of the critical temperature are studied using transition path sampling of single spin flip Monte Carlo dynamics. Analysis of the transition state ensemble (TSE) indicates that the critical nuclei are rough and anisotropic. The TSE, projected onto the free energy surface characterized by cluster size, N, and surface area, S, indicates the significance of other variables in addition to these two traditional reaction coordinates for nucleation. The transmission coefficient along N is ~ 0.35, and this reduction of the transmission coefficient from unity is explained in terms of the stochastic nature of the dynamic model.

cond-mat.stat-mech↗
arXiv2004

Micelle Formation and the Hydrophobic Effect

The tendency of amphiphilic molecules to form micelles in aqueous solution is a consequence of the hydrophobic effect. The fundamental difference between micelle assembly and macroscopic phase separation is the stoichiometric constraint that frustrates the demixing of polar and hydrophobic groups. We present a theory for micelle assembly that combines the account of this constraint with a description of the hydrophobic driving force. The latter arises from the length scale dependence of aqueous solvation. The theoretical predictions for temperature dependence and surfactant chain length dependence of critical micelle concentrations for nonionic surfactants agree favorably with experiment.

cond-mat.soft↗
arXiv2003

Excitation lines and the breakdown of Stokes-Einstein relations in supercooled liquids

By applying the concept of dynamical facilitation and analyzing the excitation lines that result from this facilitation, we investigate the origin of decoupling of transport coefficients in supercooled liquids. We illustrate our approach with two classes of models. One depicts diffusion in a strong glass former, and the other in a fragile glass former. At low temperatures, both models exhibit violation of the Stokes-Einstein relation, $D\simτ^{-1}$, where $D$ is the self diffusion constant and $τ$ is the structural relaxation time. In the strong case, the violation is sensitive to dimensionality $d$, going as $D\simτ^{-2/3}$ for $d=1$, and as $D\sim τ^{-0.95}$ for $d=3$. In the fragile case, however, we argue that dimensionality dependence is weak, and show that for $d=1$, $D \sim τ^{-0.73}$. This scaling for the fragile case compares favorably with the results of a recent experimental study for a three-dimensional fragile glass former.

cond-mat.stat-mech↗
arXiv2003

Coarse-grained microscopic model of glass formers

We introduce a coarse-grained model for atomic glass formers. Its elements are physically motivated local microscopic dynamical rules parameterized by observables. Results of the model are established and used to interpret the measured behaviors of supercooled fluids approaching glass transitions. The model predicts the presence of a crossover from hierarchical super-Arrhenius dynamics at short length scales to diffusive Arrhenius dynamics at large length scales. This prediction distinguishes our model from other theories of glass formers and can be tested by experiment.

cond-mat.stat-mech↗
arXiv2002

Drying Induced Hydrophobic Polymer Collapse

We have used computer simulation to study the collapse of a hydrophobic chain in water. We find that the mechanism of collapse is much like that of a first order phase transition. The evaporation of water in the vicinity of the polymer provides the driving force for collapse, and the rate limiting step is the nucleation of a sufficiently large vapor bubble. The study is made possible through the application of transition path sampling and a coarse grained treatment of liquid water. Relevance of our findings to understanding the folding and assembly of proteins is discussed.

cond-mat.soft↗
arXiv2002

Geometrical explanation and scaling of dynamical heterogeneities in glass forming systems

We show how dynamical heterogeneities in glass forming systems emerge as a consequence of the existence of dynamical constraints, and we offer an interpretation of the glass transition as an entropy crisis in trajectory space (space-time) rather than in configuration space. To illustrate our general ideas, we analyze the one dimensional (d=1) Fredrickson-Andersen and East models. Dynamics of such dynamically constrained systems are shown to be isomorphic to the statics of d+1 dimensional dense mixtures of polydisperse non-interpenetrating domains. The domains coincide with arrested regions in trajectory space.

cond-mat.stat-mech↗
arXiv2001

Model of a fluid at small and large length scales and the hydrophobic effect

We present a statistical field theory to describe large length scale effects induced by solutes in a cold and otherwise placid liquid. The theory divides space into a cubic grid of cells. The side length of each cell is of the order of the bulk correlation length of the bulk liquid. Large length scale states of the cells are specified with an Ising variable. Finer length scale effects are described with a Gaussian field, with mean and variance affected by both the large length scale field and by the constraints imposed by solutes. In the absence of solutes and corresponding constraints, integration over the Gaussian field yields an effective lattice gas Hamiltonian for the large length scale field. In the presence of solutes, the integration adds additional terms to this Hamiltonian. We identify these terms analytically. They can provoke large length scale effects, such as the formation of interfaces and depletion layers. We apply our theory to compute the reversible work to form a bubble in liquid water, as a function of the bubble radius. Comparison with molecular simulation results for the same function indicates that the theory is reasonably accurate. Importantly, simulating the large length scale field involves binary arithmetic only. It thus provides a computationally convenient scheme to incorporate explicit solvent dynamics and structure in simulation studies of large molecular assemblies.

cond-mat.stat-mech↗