Thermodynamic scaling of diffusion in supercooled Lennard-Jones liquids

The manner in which the intermolecular potential u(r) governs structural relaxation in liquids is a long standing problem in condensed matter physics. Herein we show that diffusion coefficients for simulated Lennard-Jones m-6 liquids (8<m<36) in normal and moderately supercooled states are a unique function of the variable rho^g/T, where rho is density and T is temperature. The scaling exponent g is a material specific constant whose magnitude is related to the steepness of the repulsive part of u(r), evaluated around the distance of closest approach between particles probed in the supercooled regime. Approximations of u(r) in terms of inverse power laws are also discussed.Comment: 4 pages, 3 figure

Understanding fragility in supercooled Lennard-Jones mixtures. II. Potential energy surface

We numerically investigated the connection between isobaric fragility and the properties of high-order stationary points of the potential energy surface in different supercooled Lennard-Jones mixtures. The increase of effective activation energies upon supercooling appears to be driven by the increase of average potential energy barriers measured by the energy dependence of the fraction of unstable modes. Such an increase is sharper, the more fragile is the mixture. Correlations between fragility and other properties of high-order stationary points, including the vibrational density of states and the localization features of unstable modes, are also discussed.Comment: 13 pages, 13 figures, minor revisions, one figure adde

Pressure-energy correlations and thermodynamic scaling in viscous Lennard-Jones liquids

We use molecular dynamics simulation results on viscous binary Lennard-Jones mixtures to examine the correlation between the potential energy and the virial. In accord with a recent proposal [U. R. Pedersen et. al. Phys. Rev. Lett. 100, 015701 (2008)], the fluctuations in the two quantities are found to be strongly correlated, exhibiting a proportionality constant, Gamma, numerically equal to one-third the slope of an inverse power law approximation to the intermolecular potential function. The correlation is stronger at higher densities, where interatomic separations are in the range where the inverse power law approximation is more accurate. These same liquids conform to thermodynamic scaling of their dynamics, with the scaling exponent equal to Gamma. Thus, the properties of strong correlation between energy and pressure and thermodynamic scaling both reflect the ability of an inverse power law representation of the potential to capture interesting features of the dynamics of dense, highly viscous liquids.Comment: 5 pages, 4 figures; published version, one figure remove

Density scaling in viscous liquids: From relaxation times to four-point susceptibilities

We present numerical calculations of a four-point dynamic susceptibility, chi_4(t), for the Kob-Andersen Lennard-Jones mixture as a function of temperature T and density rho. Over a relevant range of T and rho, the full t-dependence of chi_4(t) and thus the maximum in chi_4(t), which is proportional to the dynamic correlation volume, are invariant for state points for which the scaling variable rho^gamma/T is constant. The value of the material constant gamma is the same as that which superposes the relaxation time, tau, of the system versus rho^gamma/T. Thus, the dynamic correlation volume is directly related to tau for any thermodynamic condition in the regime where density scaling holds. Finally, we examine the conditions under which the density scaling properties are related to the existence of strong correlations between pressure and energy fluctuations.Comment: 5 pages, 4 figures, updated reference

Understanding fragility in supercooled Lennard-Jones mixtures. I. Locally preferred structures

We reveal the existence of systematic variations of isobaric fragility in different supercooled Lennard-Jones binary mixtures by performing molecular dynamics simulations. The connection between fragility and local structures in the bulk is analyzed by means of a Voronoi construction. We find that clusters of particles belonging to locally preferred structures form slow, long-lived domains, whose spatial extension increases by decreasing temperature. As a general rule, a more rapid growth, upon supercooling, of such domains is associated to a more pronounced super-Arrhenius behavior, hence to a larger fragility.Comment: 14 pages, 14 figures, minor revisions, one figure adde

Cluster glasses of ultrasoft particles

We present molecular dynamics (MD) simulations results for dense fluids of ultrasoft, fully-penetrable particles. These are a binary mixture and a polydisperse system of particles interacting via the generalized exponential model, which is known to yield cluster crystal phases for the corresponding monodisperse systems. Because of the dispersity in the particle size, the systems investigated in this work do not crystallize and form disordered cluster phases. The clustering transition appears as a smooth crossover to a regime in which particles are mostly located in clusters, isolated particles being infrequent. The analysis of the internal cluster structure reveals microsegregation of the big and small particles, with a strong homo-coordination in the binary mixture. Upon further lowering the temperature below the clustering transition, the motion of the clusters' centers-of-mass slows down dramatically, giving way to a cluster glass transition. In the cluster glass, the diffusivities remain finite and display an activated temperature dependence, indicating that relaxation in the cluster glass occurs via particle hopping in a nearly arrested matrix of clusters. Finally we discuss the influence of the microscopic dynamics on the transport properties by comparing the MD results with Monte Carlo simulations.Comment: 17 pages, 23 figure

Are there localized saddles behind the heterogeneous dynamics of supercooled liquids?

We numerically study the interplay between heterogeneous dynamics and properties of negatively curved regions of the potential energy surface in a model glassy system. We find that the unstable modes of saddles and quasi-saddles undergo a localization transition close to the Mode-Coupling critical temperature. We also find evidence of a positive spatial correlation between clusters of particles having large displacements in the unstable modes and dynamical heterogeneities.Comment: 7 pages, 3 figures, submitted to Europhys. Let

Dynamics in binary cluster crystals

As a result of the application of coarse-graining procedures to describe complex fluids, the study of systems consisting of particles interacting through bounded, repulsive pair potentials has become of increasing interest in the last years. A well known example is the so-called Generalized Exponential Model (GEM-$m$), for which the interaction between particles is described by the potential $v(r)=\epsilon\exp[-(r/\sigma)^m]$. Interactions with $m > 2$ lead to the formation of a novel phase of soft matter consisting of cluster crystals. Recent studies on the phase behavior of binary mixtures of GEM-$m$ particles have provided evidence for the formation of novel kinds of alloys, depending on the cross interactions between the two species. This work aims to study the dynamic behavior of such binary mixtures by means of extensive molecular dynamics simulations, and in particular to investigate the effect of the addition of non-clustering particles on the dynamic scenario of one-component cluster crystals. Analogies and differences with the one-component case are revealed and discussed by analyzing self- and collective dynamic correlators.Comment: 17 pages, 8 figures, submitted to JSTA

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