Mobile Particle Clusters Research Articles

Dynamic heterogeneity, cooperative motion, and Johari-Goldstein [Formula: see text]-relaxation in a metallic glass-forming material exhibiting a fragile-to-strong transition.

We investigate the Johari-Goldstein (JG) [Formula: see text]-relaxation process in a model metallic glass-forming (GF) material ([Formula: see text]), previously studied extensively by both frequency-dependent mechanical measurements and simulation studies devoted to equilibrium properties, by molecular dynamics simulations based on validated and optimized interatomic potentials with the primary aim of better understanding the nature of this universal relaxation process from a dynamic heterogeneity (DH) perspective. The present relatively low temperature and long-time simulations reveal a direct correspondence between the JG [Formula: see text]-relaxation time [Formula: see text] and the lifetime of the mobile particle clusters [Formula: see text], defined as in previous DH studies, a relationship dual to the corresponding previously observed relationship between the [Formula: see text]-relaxation time [Formula: see text] and the lifetime of immobile particle clusters [Formula: see text]. Moreover, we find that the average diffusion coefficient D nearly coincides with [Formula: see text] of the smaller atomic species (Al) and that the 'hopping time' associated with D coincides with [Formula: see text] to within numerical uncertainty, both trends being in accord with experimental studies. This indicates that the JG [Formula: see text]-relaxation is dominated by the smaller atomic species and the observation of a direct relation between this relaxation process and rate of molecular diffusion in GF materials at low temperatures where the JG [Formula: see text]-relaxation becomes the prevalent mode of structural relaxation. As an unanticipated aspect of our study, we find that [Formula: see text] exhibits fragile-to-strong (FS) glass formation, as found in many other metallic GF liquids, but this fact does not greatly alter the geometrical nature of DH in this material and the relation of DH to dynamical properties. On the other hand, the temperature dependence of the DH and dynamical properties, such as the structural relaxation time, can be significantly altered from 'ordinary' GF liquids.

Universal nature of dynamic heterogeneity in glass-forming liquids: A comparative study of metallic and polymeric glass-forming liquids.

Glass-formation is a ubiquitous phenomenon that is often observed in a broad class of materials ranging from biological matter to commonly encountered synthetic polymer, as well as metallic and inorganic glass-forming (GF) materials. Despite the many regularities in the dynamical properties of GF materials, the structural origin of the universal dynamical properties of these materials has not yet been identified. Recent simulations of coarse-grained polymeric GF liquids have indicated the coexistence of clusters of mobile and immobile particles that appear to be directly linked, respectively, to the rate of molecular diffusion and structural relaxation. The present work examines the extent to which these distinct types of "dynamic heterogeneity" (DH) arise in metallic GF liquids (Cu-Zr, Ni-Nb, and Pd-Si alloys) having a vastly different molecular structure and chemistry. We first identified mobile and immobile particles and their transient clusters and found the DH in the metallic alloys to be remarkably similar in form to polymeric GF liquids, confirming the "universality" of the DH phenomenon. Furthermore, the lifetime of the mobile particle clusters was found to be directly related to the rate of diffusion in these materials, while the lifetime of immobile particles was found to be proportional to the structural relaxation time, providing some insight into the origin of decoupling in GF liquids. An examination of particles having a locally preferred atomic packing, and clusters of such particles, suggests that there is no one-to-one relation between these populations of particles so that an understanding of the origin of DH in terms of static fluid structure remains elusive.

Localized Excitations and the Morphology of Cooperatively Rearranging Regions in a Colloidal Glass-Forming Liquid.

We develop a scheme based on a real space microscopic analysis of particle dynamics to ascertain the relevance of dynamical facilitation as a mechanism of structural relaxation in glass-forming liquids. By analyzing the spatial organization of localized excitations within clusters of mobile particles in a colloidal glass former and examining their partitioning into shell-like and corelike regions, we establish the existence of a crossover from a facilitation-dominated regime at low area fractions to a collective activated hopping-dominated one close to the glass transition. This crossover occurs in the vicinity of the area fraction at which the peak of the mobility transfer function exhibits a maximum and the morphology of cooperatively rearranging regions changes from stringlike to a compact form. Collectively, our findings suggest that dynamical facilitation is dominated by collective hopping close to the glass transition, thereby constituting a crucial step towards identifying the correct theoretical scenario for glass formation.

The relationship of dynamical heterogeneity to the Adam-Gibbs and random first-order transition theories of glass formation

We carefully examine common measures of dynamical heterogeneity for a model polymer melt and test how these scales compare with those hypothesized by the Adam and Gibbs (AG) and random first-order transition (RFOT) theories of relaxation in glass-forming liquids. To this end, we first analyze clusters of highly mobile particles, the string-like collective motion of these mobile particles, and clusters of relative low mobility. We show that the time scale of the high-mobility clusters and strings is associated with a diffusive time scale, while the low-mobility particles' time scale relates to a structural relaxation time. The difference of the characteristic times for the high- and low-mobility particles naturally explains the well-known decoupling of diffusion and structural relaxation time scales. Despite the inherent difference of dynamics between high- and low-mobility particles, we find a high degree of similarity in the geometrical structure of these particle clusters. In particular, we show that the fractal dimensions of these clusters are consistent with those of swollen branched polymers or branched polymers with screened excluded-volume interactions, corresponding to lattice animals and percolation clusters, respectively. In contrast, the fractal dimension of the strings crosses over from that of self-avoiding walks for small strings, to simple random walks for longer, more strongly interacting, strings, corresponding to flexible polymers with screened excluded-volume interactions. We examine the appropriateness of identifying the size scales of either mobile particle clusters or strings with the size of cooperatively rearranging regions (CRR) in the AG and RFOT theories. We find that the string size appears to be the most consistent measure of CRR for both the AG and RFOT models. Identifying strings or clusters with the "mosaic" length of the RFOT model relaxes the conventional assumption that the "entropic droplets" are compact. We also confirm the validity of the entropy formulation of the AG theory, constraining the exponent values of the RFOT theory. This constraint, together with the analysis of size scales, enables us to estimate the characteristic exponents of RFOT.

Determining the heterogeneity in time of the dynamics within a slowly relaxing region of a supercooled liquid: Role of sharp relaxation events

Supercooled liquids have been shown to be dynamically heterogeneous with different regions of the system presenting dynamics that vary from each other even by orders of magnitude. Computer simulations have confirmed such a picture by detecting that the mobile particles in model glass formers are not homogeneously distributed within the system but arranged in clusters. More recently, the dynamics of small systems has been characterized by demonstrating that their structural relaxation is not homogeneous in time, in the sense that it does not evolve gradually but it is signed by rapid bursts of mobility characterized by relative compact clusters of mobile particles. These events (which have been named d clusters) are fast and sparse and trigger the transitions the system experiences between metabasins (MB) of its potential-energy surface. The MB residence times are much larger than the time scales of occurrence of the d clusters, and it has been suggested that the events that occur within them scarcely contribute to the structural relaxation of the system. Thus, the picture of glassy relaxation that emerges would indicate that at any time a supercooled liquid may present different spatial regions, each one characterized by different structural relaxation times. In turn, each of such regions would not relax smoothly or gradually but by means of sporadic sharp relaxation events. Here, we assess for a model glass former the relative relevance of the MB exploration events and of the d clusters both in small systems and within regions of large systems, to show that the structural relaxation at the region level is indeed extremely heterogeneous in time and utterly governed by the latter.

Spatially Heterogeneous Dynamics and the Adam−Gibbs Relation in the Dzugutov Liquid

We perform molecular dynamics simulations of a one-component glass-forming liquid and use the inherent structure formalism to test the predictions of the Adam-Gibbs (AG) theory and to explore the possible connection between these predictions and spatially heterogeneous dynamics. We calculate the temperature dependence of the average potential energy of the equilibrium liquid and show that it obeys the Rosenfeld-Tarazona T(3/5) law for low temperature T, while the average inherent structure energy is found to be inversely proportional to temperature at low T, consistent with a Gaussian distribution of potential energy minima. We investigate the shape of the basins around the local minima in configuration space via the average basin vibrational frequency and show that the basins become slightly broader upon cooling. We evaluate the configurational entropy S(conf), a measure of the multiplicity of potential energy minima sampled by the system, and test the validity of the AG relation between S(conf) and the bulk dynamics. We quantify the dynamically heterogeneous motion by analyzing the motion of particles that are mobile on short and intermediate time scales relative to the characteristic bulk relaxation time. These mobile particles move in one-dimensional "strings", and these strings form clusters with a well-defined average cluster size. The AG approach predicts that the minimum size of cooperatively rearranging regions (CRR) of molecules is inversely proportional to S(conf), and recently (Phys. Rev. Lett. 2003, 90, 085506) it has been shown that the mobile-particle clusters are consistent with the CRR envisaged by Adam and Gibbs. We test the possibility that the mobile-particle strings, rather than clusters, may describe the CRR of the Adam-Gibbs approach. We find that the strings also follow a nearly inverse relation with S(conf). We further show that the logarithm of the time when the strings and clusters are maximum, which occurs in the late-beta-relaxation regime of the intermediate scattering function, follows a linear relationship with 1/TS(conf), in agreement with the AG prediction for the relationship between the configurational entropy and the characteristic time for the liquid to undergo a transition to a new configuration. Since strings are the basic elements of the clusters, we propose that strings are a more appropriate measure of the minimum size of a CRR that leads to configurational transitions. That the cluster size also has an inverse relationship with S(conf) may be a consequence of the fact that the clusters are composed of strings.

Dynamic Heterogeneities in Supercooled Water

We investigate dynamic heterogeneities in liquid water by performing molecular dynamics simulations of the SPC/E model. We find clusters of mobile molecules. We study the temperature and time dependence of the cluster size and find that clusters grow as temperature decreases and have a maximum size at the time scale corresponding to the escape of the molecules from the cage formed by neighboring molecules. We relate the average mass n* of mobile particle clusters to the diffusion constant, D, and the configurational entropy, Sconf. We find that n* can be interpreted as the mass of the “cooperatively rearranging regions” hypothesized in the Adam−Gibbs theory of the dynamics of supercooled liquids. In the context of the potential energy landscape (PEL) approach, the diffusion of molecules is related to the change of basins. By studying the dynamics of the system on the PEL, we identify clusters formed by the molecules with large displacements as the system visits consecutive local minima on the PEL. We relate the changing of basins with the restructuring of the hydrogen bond network.

Formation of Transient Clusters on Nanoscopic Length Scales in a Simulated One-Component Supercooled Liquid

Dense liquids above their glass transition exhibit spatially heterogeneous dynamics in which regions within the liquid exhibit enhanced or diminished mobility relative to the average on some time scale. Substantial evidence suggests that these regions are confined to nanoscopic sizes at temperatures close to the mode coupling temperature T MCT, and reach well beyond the characteristic length scale over which the two-point static structure of the liquid is correlated. In this paper, we investigate the formation of clusters of mobile particles in a dynamically heterogeneous model liquid. We find that clusters are formed as a result of mobility propagation that begins from distributed locations confined within a nanoscopic local structure. This mobility is facilitated through the development of quasi-one dimensional string-like rearrangements within the nanoscopic region.

Time evolution of clusters of mobile particles in a model glass former

In this work we investigate by means of molecular dynamics simulations the detailed time evolution of string-like cooperative motions in a binary Lennard–Jones system at temperatures close to its mode-coupling temperature, T c. The strings will be fully geometrically and dynamically characterised, making evident the correlated and concerted nature of the motions of the particles comprised. We shall show that at low temperature each string occurs in a sharp time window within the time interval [0,t ∗] , where t ∗ is a characteristic time related to the lifetime of the global clusters of mobile particles. Moreover, the different strings that comprise a given global cluster will be shown to take place independently and asynchronically, thus providing further support to the heterogeneous scenario of relaxation, but in which different independent string-like sub-regions relax at different timescales. Finally, we shall also demonstrate that as temperature is increased the strings evolve during an increasing fraction of the time interval [0,t ∗] and that for T∼0.55 the lifetimes of the strings and of the global clusters become akin to each other.

Connection between Adam-Gibbs theory and spatially heterogeneous dynamics.

We investigate the spatially heterogeneous dynamics in the extended simple point charge model of water using molecular dynamics simulations. We relate the average mass n* of mobile particle clusters to the diffusion constant and the configurational entropy. Hence, n* can be interpreted as the mass of the "cooperatively rearranging regions" that form the basis of the Adam-Gibbs theory of the dynamics of supercooled liquids. We also examine the time and temperature dependence of these transient clusters.