Universal localization transition accompanying glass formation: insights from efficient molecular dynamics simulations of diverse supercooled liquids (original) (raw)
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Understanding Slow and Heterogeneous Dynamics in Model Supercooled Glass-Forming Liquids
ACS Omega
Glasses are ubiquitous in nature. Many common items such as ketchups, cosmetic products, toothpaste, etc. and metallic glasses are examples of such glassy materials whose dynamical and rheological properties matter in our daily life. The dynamics of these glass-forming systems are known to be very sluggish and heterogeneous, but a detailed understanding of the origin of such slowing down is still lacking. Slow heterogeneous dynamics occur in a wide variety of systems at scales ranging from microscopic to macroscopic. Polymeric liquids, granular material, such as powder and sand, gels, and foams and also metallic alloys show such complex glassy dynamics at appropriate conditions. Recently, the existence of dynamical heterogeneity has also been found in biological systems starting from collective cell migration in a monolayer of cells to embryonic morphogenesis, cancer invasion, and wound healing. Extensive research in the past decade or so lead to the understanding that there are growing dynamic and static correlation lengths associated with the observed dynamical heterogeneity and rapid rise in viscosity. In this review, we have highlighted the recent developments on measuring these correlation lengths in glass-forming liquids and their possible implications in the physics of the glass transition.
Atomic mechanism of glass formation in supercooled monatomic liquids
Solid State Communications, 2010
Atomic mechanism of glass formation in supercooled monatomic liquids is monitored via analyzing the spatial arrangement of solid-like atoms. The supercooled states are obtained by cooling from the melt using molecular dynamics (MD) simulation. Solid-like atoms, detected via Lindemann-like freezing criterion, are found throughout the liquid. Their number increases with decreasing temperature and they form clusters. In the deeply supercooled region, all solid-like atoms form a single percolation cluster which spans throughout the system. The number of atoms in this cluster increases steeply with further cooling. Glass formation in supercooled liquids occurs when a single percolation cluster of solid-like atoms involves the majority of atoms in the system to form a relatively rigid glassy solid. By analyzing the temperature dependence of static and dynamic properties, we identify three characteristic temperatures of glass formation in supercooled liquids including the Vogel-Fulcher temperature.
Anomalous diffusion in supercooled liquids: A long-range localization in particle trajectories
The Journal of Chemical Physics, 2009
A statistical analysis of the geometries of particle trajectories in the supercooled liquid state is reported. We examine two structurally different fragile glass-forming liquids simulated by molecular dynamics. In both liquids, the trajectories are found to exhibit a long-range localisation distinct from the short-range localisation within the cage of nearest neighbours. This novel diffusion anomaly is interpreted as a result of the potential-energy landscape topography of fragile glass-formers where the local energy minima coalesce into metabasins -compact domains with low escape probability.
Crystal nucleation in a supercooled liquid with glassy dynamics
Physical review letters, 2009
In simulations of supercooled, high-density liquid silica we study a range of temperature T in which we find both crystal nucleation, as well as the characteristic dynamics of a glass forming liquid, including a breakdown of the Stokes-Einstein relation. We find that the liquid cannot be observed below a homogeneous nucleation limit (HNL) at which the liquid crystallizes faster than it can equilibrate. We show that the HNL would occur at lower T , and perhaps not at all, if the Stokes-Einstein relation were obeyed, and hence that glassy dynamics plays a central role in setting a crystallization limit on the liquid state in this case. We also explore the relation of the HNL to the Kauzmann temperature, and test for spinodal-like effects near the HNL.
Supercooled Lennard-Jones liquids and glasses: a kinetic Monte Carlo approach
Journal of Non-Crystalline Solids, 2004
A kinetic Monte Carlo (KMC) method is used to study the structural properties and dynamics of a supercooled binary Lennard-Jones liquid around the glass transition temperature. This technique permits us to explore the potential energy surface and barrier distributions without suffering the exponential slowing down at low temperature that affects molecular dynamics simulations. In agreement with previous studies we observe a distinct change in behaviour around T = 0.45, close to the dynamical transition temperature T c of mode coupling theory (MCT). Below this temperature the number of different local minima visited by the system for the same number of KMC steps decreases by more than an order of magnitude. The mean number of atoms involved in each jump between local minima and the average distance they move also decreases significantly, and new features appear in the partial structure factor. Above T ∼ 0.45 the probability distribution for the magnitude of the atomic displacement per KMC step exhibits an exponential decay, which is only weakly temperature dependent.
Orientational relaxation (OR) in a viscous, glassy liquid is investigated by carrying out extensive NPT molecular dynamics simulations of isolated ellipsoids in a glass forming binary mixture. Near the glass transition, the OR occurs mainly via correlated hopping, sometimes involving participation of several neighboring atoms, placed in a ring like tunnel. In the glassy state, hopping is found to be accompanied by larger fluctuations in the total energy and the volume of the system. Both orientational and translational hopping are found to be gated, restricted primarily by the entropic bottlenecks, with orientation becoming increasingly slower than translation as the pressure is increased. OR is heterogeneous, with a wide distribution of decay times.
Physical Review E, 2012
We develop a framework for understanding the difference between strong and fragile behavior in the dynamics of glass-forming liquids from the properties of the potential energy landscape. Our approach is based on a master equation description of the activated jump dynamics among the local minima of the potential energy (the so-called inherent structures) that characterize the potential energy landscape of the system. We study the dynamics of a small atomic cluster using this description as well as molecular dynamics simulations and demonstrate the usefulness of our approach for this system. Many of the remarkable features of the complex dynamics of glassy systems emerge from the activated dynamics in the potential energy landscape of the atomic cluster. The dynamics of the system exhibits typical characteristics of a strong supercooled liquid when the system is allowed to explore the full configuration space. This behavior arises because the dynamics is dominated by a few lowest-lying minima of the potential energy and the potential energy barriers between these minima. When the system is constrained to explore only a limited region of the potential energy landscape that excludes the basins of attraction of a few lowest-lying minima, the dynamics is found to exhibit the characteristics of a fragile liquid.
Dynamics and thermodynamics of supercooled liquids and glasses from a model energy landscape
Physical Review B, 2001
The dynamics and thermodynamics of a model potential-energy surface are analyzed with regard to supercooling and glass formation. Relaxation is assumed to be mediated by pathways that connect groups of local minima. The dynamics between these groups is treated via transition state theory using appropriate densities of states consistent with the thermodynamics of the model, with a general expression for the free energy barrier. Nonergodicity is admitted by successive disconnection of regions that no longer contribute to the partition function as a function of the observation time scale. The model exhibits properties typical of supercooled liquids and glasses spanning the whole range of ''fragile'' and ''strong'' behavior. Non-Arrhenius dynamics, characteristic of ''fragile'' glass formers, are observed when the barriers to relaxation increase as the potential energy decreases, but only if the observation time scale is long enough. For a fixed observation time, fragility generally increases as the free energy barriers decrease and vibrational frequencies increase. We associate higher vibrational frequencies with systems that have more local minima, and hence when the model exhibits dynamic fragility we usually see a large change in the heat capacity at the glass transition. However, in some regions of parameter space the expected correlations between dynamics and thermodynamics are not present.