Kinetics in one-dimensional lattice gas and Ising models from time-dependent density functional theory

Time-dependent density functional theory, proposed recently in the context of atomic diffusion and non-equilibrium processes in solids, is tested against Monte Carlo simulation. In order to assess the basic approximation of that theory, the representation of non-equilibrium states by a local equilibrium distribution function, we focus on one-dimensional lattice models, where all equilibrium properties can be worked exactly from the known free energy as a functional of the density. This functional determines the thermodynamic driving forces away from equilibrium. In our studies of the interfacial kinetics of atomic hopping and spin relaxation, we find excellent agreement with simulations, suggesting that the method is useful also for treating more complex problems.Comment: 8 pages, 5 figures, submitted to Phys. Rev.

Largest Lyapunov Exponent for Many Particle Systems at Low Densities

The largest Lyapunov exponent $\lambda^+$ for a dilute gas with short range interactions in equilibrium is studied by a mapping to a clock model, in which every particle carries a watch, with a discrete time that is advanced at collisions. This model has a propagating front solution with a speed that determines $\lambda^+$, for which we find a density dependence as predicted by Krylov, but with a larger prefactor. Simulations for the clock model and for hard sphere and hard disk systems confirm these results and are in excellent mutual agreement. They show a slow convergence of $\lambda^+$ with increasing particle number, in good agreement with a prediction by Brunet and Derrida.Comment: 4 pages, RevTeX, 2 Figures (encapsulated postscript). Submitted to Phys. Rev. Let

Chaotic Properties of Dilute Two and Three Dimensional Random Lorentz Gases I: Equilibrium Systems

We compute the Lyapunov spectrum and the Kolmogorov-Sinai entropy for a moving particle placed in a dilute, random array of hard disk or hard sphere scatterers - i.e. the dilute Lorentz gas model. This is carried out in two ways: First we use simple kinetic theory arguments to compute the Lyapunov spectrum for both two and three dimensional systems. In order to provide a method that can easily be generalized to non-uniform systems we then use a method based upon extensions of the Lorentz-Boltzmann (LB) equation to include variables that characterize the chaotic behavior of the system. The extended LB equations depend upon the number of dimensions and on whether one is computing positive or negative Lyapunov exponents. In the latter case the extended LB equation is closely related to an "anti-Lorentz-Boltzmann equation" where the collision operator has the opposite sign from the ordinary LB equation. Finally we compare our results with computer simulations of Dellago and Posch and find very good agreement.Comment: 48 pages, 3 ps fig

Molecular mode-coupling theory for supercooled liquids: Application to water

We present mode-coupling equations for the description of the slow dynamics observed in supercooled molecular liquids close to the glass transition. The mode-coupling theory (MCT) originally formulated to study the slow relaxation in simple atomic liquids, and then extended to the analysis of liquids composed by linear molecules, is here generalized to systems of arbitrarily shaped, rigid molecules. We compare the predictions of the theory for the $q$-vector dependence of the molecular nonergodicity parameters, calculated by solving numerically the molecular MCT equations in two different approximation schemes, with ``exact'' results calculated from a molecular dynamics simulation of supercooled water. The agreement between theory and simulation data supports the view that MCT succeeds in describing the dynamics of supercooled molecular liquids, even for network forming ones.Comment: 22 pages 4 figures Late

Thermodynamic formalism for systems with Markov dynamics

The thermodynamic formalism allows one to access the chaotic properties of equilibrium and out-of-equilibrium systems, by deriving those from a dynamical partition function. The definition that has been given for this partition function within the framework of discrete time Markov chains was not suitable for continuous time Markov dynamics. Here we propose another interpretation of the definition that allows us to apply the thermodynamic formalism to continuous time. We also generalize the formalism --a dynamical Gibbs ensemble construction-- to a whole family of observables and their associated large deviation functions. This allows us to make the connection between the thermodynamic formalism and the observable involved in the much-studied fluctuation theorem. We illustrate our approach on various physical systems: random walks, exclusion processes, an Ising model and the contact process. In the latter cases, we identify a signature of the occurrence of dynamical phase transitions. We show that this signature can already be unravelled using the simplest dynamical ensemble one could define, based on the number of configuration changes a system has undergone over an asymptotically large time window.Comment: 64 pages, LaTeX; version accepted for publication in Journal of Statistical Physic

Light scattering spectra of supercooled molecular liquids

The light scattering spectra of molecular liquids are derived within a generalized hydrodynamics. The wave vector and scattering angle dependences are given in the most general case and the change of the spectral features from liquid to solidlike is discussed without phenomenological model assumptions for (general) dielectric systems without long-ranged order. Exact microscopic expressions are derived for the frequency-dependent transport kernels, generalized thermodynamic derivatives and the background spectra.Comment: 12 page

Simple deterministic dynamical systems with fractal diffusion coefficients

We analyze a simple model of deterministic diffusion. The model consists of a one-dimensional periodic array of scatterers in which point particles move from cell to cell as defined by a piecewise linear map. The microscopic chaotic scattering process of the map can be changed by a control parameter. This induces a parameter dependence for the macroscopic diffusion coefficient. We calculate the diffusion coefficent and the largest eigenmodes of the system by using Markov partitions and by solving the eigenvalue problems of respective topological transition matrices. For different boundary conditions we find that the largest eigenmodes of the map match to the ones of the simple phenomenological diffusion equation. Our main result is that the difffusion coefficient exhibits a fractal structure by varying the system parameter. To understand the origin of this fractal structure, we give qualitative and quantitative arguments. These arguments relate the sequence of oscillations in the strength of the parameter-dependent diffusion coefficient to the microscopic coupling of the single scatterers which changes by varying the control parameter.Comment: 28 pages (revtex), 12 figures (postscript), submitted to Phys. Rev.

Frequency dependent specific heat of viscous silica

We apply the Mori-Zwanzig projection operator formalism to obtain an expression for the frequency dependent specific heat c(z) of a liquid. By using an exact transformation formula due to Lebowitz et al., we derive a relation between c(z) and K(t), the autocorrelation function of temperature fluctuations in the microcanonical ensemble. This connection thus allows to determine c(z) from computer simulations in equilibrium, i.e. without an external perturbation. By considering the generalization of K(t) to finite wave-vectors, we derive an expression to determine the thermal conductivity \lambda from such simulations. We present the results of extensive computer simulations in which we use the derived relations to determine c(z) over eight decades in frequency, as well as \lambda. The system investigated is a simple but realistic model for amorphous silica. We find that at high frequencies the real part of c(z) has the value of an ideal gas. c'(\omega) increases quickly at those frequencies which correspond to the vibrational excitations of the system. At low temperatures c'(\omega) shows a second step. The frequency at which this step is observed is comparable to the one at which the \alpha-relaxation peak is observed in the intermediate scattering function. Also the temperature dependence of the location of this second step is the same as the one of the $\alpha-$peak, thus showing that these quantities are intimately connected to each other. From c'(\omega) we estimate the temperature dependence of the vibrational and configurational part of the specific heat. We find that the static value of c(z) as well as \lambda are in good agreement with experimental data.Comment: 27 pages of Latex, 8 figure

Dynamical field theory for glass-forming liquids, self-consistent resummations and time-reversal symmetry

We analyse the symmetries and the self-consistent perturbative approaches of dynamical field theories for glassforming liquids. In particular, we focus on the time-reversal symmetry (TRS), which is crucial to obtain fluctuation-dissipation relations (FDRs). Previous field theoretical treatment violated this symmetry, whereas others pointed out that constructing symmetry preserving perturbation theories is a crucial and open issue. In this work we solve this problem and then apply our results to the mode-coupling theory of the glass transition (MCT). We show that in the context of dynamical field theories for glass-forming liquids TRS is expressed as a nonlinear field transformation that leaves the action invariant. Because of this nonlinearity, standard perturbation theories generically do not preserve TRS and in particular FDRs. We show how one can cure this problem and set up symmetry-preserving perturbation theories by introducing some auxiliary fields. As an outcome we obtain Schwinger-Dyson dynamical equations that automatically preserve FDRs and that serve as a basis for carrying out symmetry-preserving approximations. We apply our results to MCT, revisiting previous field theory derivations of MCT equations and showing that they generically violate FDR. We obtain symmetry-preserving mode-coupling equations and discuss their advantages and drawbacks. Furthermore, we show, contrary to previous works, that the structure of the dynamic equations is such that the ideal glass transition is not cut off at any finite order of perturbation theory, even in the presence of coupling between current and density. The opposite results found in previous field theoretical works, such as the ones based on nonlinear fluctuating hydrodynamics, were only due to an incorrect treatment of TRS.Comment: 54 pages, 21 figure