Implicit Finite-Size Effects in Computer Simulations

The influence of periodic boundary conditions (implicit finite-size effects) on the anisotropy of pair correlations in computer simulations is studied for a dense classical fluid of pair-wise interacting krypton atoms near the triple point. Molecular dynamics simulation data for the pair distribution function of N-particle systems, as a function of radial distance, polar angle, and azimuthal angle are compared directly with corresponding theoretical predictions [L. R. Pratt and S. W. Haan, J. Chem. Phys. 74, 1864 (1981)]. For relatively small systems of N=60, 80, and 108 atoms, significant angular variation is observed, which is qualitatively, and in several cases quantitatively, well predicted by theory. Finite-size corrections to the spherically-averaged radial distribution function, however, are found to be comparable to random statistical errors for runs of 10^5 time steps.Comment: plain TeX, 14 pages + 16 postscript figures, to appear Z. Phys.

Dynamics of a Rigid Rod in a Glassy Medium

We present simulations of the motion of a single rigid rod in a disordered static 2d-array of disk-like obstacles. The rotational, $D_{\rm R}$, and center-of-mass translational, $D_{\rm CM}$, diffusion constants are calculated for a wide range of rod length $L$ and density of obstacles $\rho$. It is found that $D_{\rm CM}$ follows the behavior predicted by kinetic theory for a hard disk with an effective radius $R(L)$. A dynamic crossover is observed in $D_{\rm R}$ for $L$ comparable to the typical distance between neighboring obstacles $d_{\rm nn}$. Using arguments from kinetic theory and reptation, we rationalize the scaling laws, dynamic exponents, and prefactors observed for $D_{\rm R}$. In analogy with the enhanced translational diffusion observed in deeply supercooled liquids, the Stokes-Einstein-Debye relation is violated for $L > 0.6d_{\rm nn}$.Comment: 8 pages, 4 figures. Major changes. To be published in Europhysics Letter

Fractional Stokes-Einstein and Debye-Stokes-Einstein relations in a network forming liquid

We study the breakdown of the Stokes-Einstein (SE) and Debye-Stokes-Einstein (DSE) relations for translational and rotational motion in a prototypical model of a network-forming liquid, the ST2 model of water. We find that the emergence of ``fractional'' SE and DSE relations at low temperature is ubiquitous in this system, with exponents that vary little over a range of distinct physical regimes. We also show that the same fractional SE relation is obeyed by both mobile and immobile dynamical heterogeneities of the liquid

Long wavelength structural anomalies in jammed systems

The structural properties of static, jammed packings of monodisperse spheres in the vicinity of the jamming transition are investigated using large-scale computer simulations. At small wavenumber $k$, we argue that the anomalous behavior in the static structure factor, $S(k) \sim k$, is consequential of an excess of low-frequency, collective excitations seen in the vibrational spectrum. This anomalous feature becomes more pronounced closest to the jamming transition, such that $S(0) \to 0$ at the transition point. We introduce an appropriate dispersion relation that accounts for these phenomena that leads us to relate these structural features to characteristic length scales associated with the low-frequency vibrational modes of these systems. When the particles are frictional, this anomalous behavior is suppressed providing yet more evidence that jamming transitions of frictional spheres lie at lower packing fractions that that for frictionless spheres. These results suggest that the mechanical properties of jammed and glassy media may therefore be inferred from measurements of both the static and dynamical structure factors.Comment: 8 pages, 6 figure captions. Completely revised version to appear in Phys. Rev.

Lattice gas with ``interaction potential''

We present an extension of a simple automaton model to incorporate non-local interactions extending over a spatial range in lattice gases. {}From the viewpoint of Statistical Mechanics, the lattice gas with interaction range may serve as a prototype for non-ideal gas behavior. {}From the density fluctuations correlation function, we obtain a quantity which is identified as a potential of mean force. Equilibrium and transport properties are computed theoretically and by numerical simulations to establish the validity of the model at macroscopic scale.Comment: 12 pages LaTeX, figures available on demand ([email protected]

Adding Salt to an Aqueous Solution of t-Butanol: Is Hydrophobic Association Enhanced or Reduced?

Recent neutron scattering experiments on aqueous salt solutions of amphiphilic t-butanol by Bowron and Finney [Phys. Rev. Lett. {\bf 89}, 215508 (2002); J. Chem. Phys. {\bf 118}, 8357 (2003)] suggest the formation of t-butanol pairs, bridged by a chloride ion via ${O}-{H}...{Cl}^-$ hydrogen-bonds, and leading to a reduced number of intermolecular hydrophobic butanol-butanol contacts. Here we present a joint experimental/theoretical study on the same system, using a combination of molecular dynamics simulations and nuclear magnetic relaxation measurements. Both theory and experiment clearly support the more intuitive scenario of an enhanced number of hydrophobic contacts in the presence of the salt, as it would be expected for purely hydrophobic solutes [J. Phys. Chem. B {\bf 107}, 612 (2003)]. Although our conclusions arrive at a structurally completely distinct scenario, the molecular dynamics simulation results are within the experimental errorbars of the Bowron and Finney work.Comment: 15 pages twocolumn revtex, 11 figure

Experimental observation of the intricate free-energy landscape for a soft glassy system

In the free energy landscape picture of glassy systems, the slow dynamics characteristic of these systems is believed to be due to the existence of a complicated free-energy landscape with many local minima. We show here that for a colloidal glassy material multiple paths can be taken through the free energy landscape, that can even lead to different 'final' non-ergodic states at the late stages of aging. We provide clear experimental evidence for the distinction of gel and glassy states in the system and show that for a range of colloid concentrations, the transition to non-ergodicity can occur in either direction (gel or glass), and may be accompanied by 'hesitations' between the two directions. This shows that colloidal gels and glasses are merely global free-energy minima in the same free energy landscape, and that the paths leading to these minima can indeed be complicated.Comment: 5 pages, 5 figure

Microscopic dynamics and relaxation processes in liquid Hydrogen Fluoride

Inelastic x-ray scattering and Brillouin light scattering measurements of the dynamic structure factor of liquid hydrogen fluoride have been performed in the temperature range$T=214\div 283 K$. The data, analysed using a viscoelastic model with a two timescale memory function, show a positive dispersion of the sound velocity $c(Q)$ between the low frequency value $c_0(Q)$ and the high frequency value $c_{\infty \alpha}(Q)$. This finding confirms the existence of a structural ($\alpha$) relaxation directly related to the dynamical organization of the hydrogen bonds network of the system. The activation energy $E_a$ of the process has been extracted by the analysis of the temperature behavior of the relaxation time $\tau_\alpha(T)$ that follows an Arrhenius law. The obtained value for $E_a$, when compared with that observed in another hydrogen bond liquid as water, suggests that the main parameter governing the $\alpha$-relaxation process is the number of the hydrogen bonds per molecule.Comment: 9 pages and 12 figure

Weak links between fast mobility and local structure in molecular and atomic liquids

We investigate by molecular-dynamics simulations, the fast mobility-the rattling amplitude of the particles temporarily trapped by the cage of the neighbors-in mildly supercooled states of dense molecular (linear trimers) and atomic (binary mixtures) liquids. The mixture particles interact by the Lennard-Jones potential. The non-bonded particles of the molecular system are coupled by the more general Mie potential with variable repulsive and attractive exponents in a range which is a characteristic of small n-alkanes and n-alcohols. Possible links between the fast mobility and the geometry of the cage (size and shape) are searched. The correlations on a per-particle basis are rather weak. Instead, if one groups either the particles in fast-mobility subsets or the cages in geometric subsets, the increase of the fast mobility with both the size and the asphericity of the cage is revealed. The observed correlations are weak and differ in states with equal relaxation time. Local forces between a tagged particle and the first-neighbour shell do not correlate with the fast mobility in the molecular liquid. It is concluded that the cage geometry alone is unable to provide a microscopic interpretation of the known, universal link between the fast mobility and the slow structural relaxation. We suggest that the particle fast dynamics is affected by regions beyond the first neighbours, thus supporting the presence of collective, extended fast modes

Three-Particle Correlations in Simple Liquids

We use video microscopy to follow the phase-space trajectory of a two-dimensional colloidal model liquid and calculate three-point correlation functions from the measured particle configurations. Approaching the fluid-solid transition by increasing the strength of the pair-interaction potential, one observes the gradual formation of a crystal-like local order due to triplet correlations, while being still deep inside the fluid phase. Furthermore, we show that in a strongly interacting system the Born-Green equation can be satisfied only with the full triplet correlation function but not with three-body distribution functions obtained from superposing pair-correlations (Kirkwood superposition approximation).Comment: 4 pages, submitted to PRL, experimental paper, 2nd version: Fig.1 and two new paragraphs have been adde