Asymptotic time behavior of correlation functions. II. Kinetic and potential terms

On the basis of the mode-coupling theory we obtain the long-time behavior t ^–d/2 for the kinetic, potential, and cross-terms in the Green-Kubo integrands, expressed completely in terms of transport coefficients and thermodynamic quantities. All two-mode amplitudes are explicitly evaluated in terms of measurable quantities such as specific heats, thermal expansion coefficients, etc.     

Nonequilibrium real time Green's functions and the condition of weakening of initial correlation

A new method is given to calculate real-time Green's functions in nonequilibrium from the hierarchy of equations of motion in connection with the boundary condition of weakening of initial correlations. The way of deriving a generalized quantum Boltzmann equation is shown.     

Kinetic theory of long time tails in velocity correlation functions in a moderately dense electron gas

The long time tails of the correlation functions that determine the self-diffusion coefficient and the kinetic parts of the shear viscosity and heat conductivity in a one-component plasma are calculated using a systematic kinetic theory. The results are in agreement with those obtained from the phenomenological mode coupling theory. The formal kinetic theory calculations of previous workers, who obtained incomplete long time tail results, are also discussed.     

Criteria for local equilibrium in a system with transport of heat and mass

Nonequilibrium molecular dynamics is used to compute the coupled heat and mass transport in a binary isotope mixture of particles interacting with a Lennard-Jones/spline potential. Two different stationary states are studied, one with a fixed internal energy flux and zero mass flux, and the other with a fixed diffusive mass flux and zero temperature gradient. Computations are made for one overall temperature,T=2, and three overall number densities,n=0.1, 0.2, and 0.4. (All numerical values are given in reduced, Lennard-Jones units unless otherwise stated.) Temperature gradients are up to T=0.09 and weight-fraction gradients up to w ₁=0.007. The flux-force relationships are found to be linear over the entire range. All four transport coefficients (theL-matrix) are determined and the Onsager reciprocal relationship for the off-diagonal coefficients is verified. Four different criteria are used to analyze the concept of local equilibrium in the nonequilibrium system. The local temperature fluctuation is found to be T0.03T and of the same order as the maximum temperature difference across the control volume, except near the cold boundary. A comparison of the local potential energy, enthalpy, and pressure with the corresponding equilibrium values at the same temperature, density, and composition also verifies that local equilibrium is established, except near the boundaries of the system. The velocity contribution to the BoltzmannH-function agrees with its Maxwellian (equilibrium) value within 1%, except near the boundaries, where the deviation is up to 4%. Our results do not support the Eyring-type transport theory involving jumps across energy barriers; we find that its estimates for the heat and mass fluxes are wrong by at least one order of magnitude.     

Entropy,information theory,and the approach to equilibrium of coupled harmonic oscillator systems

Finite segments of infinite chains of classical coupled harmonic oscillators are treated as models of thermodynamic systems in contact with a heat bath, i.e., canonical ensembles. The Liouville function for the infinite chain is reduced by integrating over the outside variables to a function _N of the variables of theN-particle segment that is the thermodynamic system. The reduced Liouville function _N which is calculated from the dynamics of the infinite chain and the statistical knowledge of the coordinates and momenta att = 0, is a time-dependent probability density in the 2N-dimensional phase space of the system. A Gibbs entropy defined in terms of _N measures the evolution of knowledge of the system (more accurately, the growth of missing pertinent information) in the sense of information theory. As ¦t ¦ , energy is equipartitioned, the entropy evolves to the value expected from equilibrium statistical mechanics, and _N evolves to an equilibrium distribution function. The simple chain exhibits diffusion in coordinate space, i.e., Brownian motion, and the diffusivity is shown to depend only on the initial distribution of momenta (not of coordinates) in the heat bath. The harmonically bound chain, in the limit of weak coupling, serves as an excellent model for the approach to equilibrium of a canonical ensemble of weakly interacting particles.     

Approach to equilibrium of coupled harmonic oscillator systems. II

The approach to equilibrium of a finite segment of an infinite chain of harmonically coupled masses is studied in several variations. The chain is taken as completely free, or it is bound atx ₀ =0; ordinary coordinates and momenta or Schrödinger variables are used to treat the dynamics; and the inital distribution of heat-bath variables is chosen to be canonical or noncanonical. Equipartition of energy is found in all cases. Brownian drifts are obtained for the free chain with ordinary variables, but when this is excluded, the equilibrium entropy is found to be canonical and extensive when the initial heat bath is canonical, but less than canonical and slightly nonextensive when the initial heat bath is noncanonical. The modifications of the entropy do not contribute to the heat capacity of the system.Supported in part by the United States Atomic Energy Commission.     

The time-local view of nonequilibrium statistical mechanics. I. Linear theory of transport and relaxation

The various approaches to nonequilibrium statistical mechanics may be subdivided into convolution and convolutionless (time-local) ones. While the former, put forward by Zwanzig, Mori, and others, are used most commonly, the latter are less well developed, but have proven very useful in recent applications. The aim of the present series of papers is to develop the time-local picture (TLP) of nonequilibrium statistical mechanics on a new footing and to consider its physical implications for topics such as the formulation of irreversible thermodynamics. The most natural approach to TLP is seen to derive from the Fourier-Laplace transform ) of pertinent time correlation functions, which on the physical sheet typically displays an essential singularity at z= and a number of macroscopic and microscopic poles in the lower half-plane corresponding to long- and short-lived modes, respectively, the former giving rise to the autonomous macrodynamics, whereas the latter are interpreted as doorway modes mediating the transfer of information from relevant to irrelevant channels. Possible implications of this doorway mode concept for socalled extended irreversible thermodynamics are briefly discussed. The pole structure is used for deriving new kinds of generalized Green-Kubo relations expressing macroscopic quantities, transport coefficients, e.g., by contour integrals over current-current correlation functions obeying Hamiltonian dynamics, the contour integration replacing projection. The conventional Green-Kubo relations valid for conserved quantities only are rederived for illustration. Moreover, may be expressed by a Laurent series expansion in positive and negative powers ofz, from which a rigorous, general, and straightforward method is developed for extracting all macroscopic quantities from so-called secularly divergent expansions of as obtained from the application of conventional many-body techniques to the calculation of . The expressions are formulated as time scale expansions, which should rapidly converge if macroscopic and microscopic time scales are sufficiently well separated, i.e., if lifetime (memory) effects are not too large.     

Local structure theory: Calculation on hexagonal arrays,and interaction of rule and lattice

Local structure theory calculations⁷ are applied to the study of cellular automata on the two-dimensional hexagonal lattice. A particular hexagonal lattice rule denoted (3422) is considered in detail. This rule has many features in common with Conway'sLife. The local structure theory captures many of the statistical properties of this rule; this supports hypotheses raised by a study ofLife itself⁽⁶⁾. As inLife, the state of a cell under (3422) depends only on the state of the cell itself and the sum of states in its neighborhood at the previous time step. This property implies that evolution rules which operate in the same way can be studied on different lattices. The differences between the behavior of these rules on different lattices are dramatic. The mean field theory cannot reflect these differences. However, a generalization of the mean field theory, the local structure theory, does account for the rule-lattice interaction.     

Microscopic theory of the long-wavelength modes of two-component plasmas and ionic liquids: III. The space-time correlation functions

The identity between the exact screening length obtained from the static charge density correlation function and the one which appears in the Einstein relation between the transport coefficients of electrical conductivity and mass diffusion is demonstrated from first principles. For the space-time correlation functions of the number densities we show that their long-wavelength behaviour is completely determined by the four hydrodynamical modes of the two-component system of neutral particles. For charged particle systems there are only three hydrodynamical modes while we have moreover to add the two charge relaxation modes in order to exhaust the long-wavelength limit of the first sum-rule. The strengths with which the various modes appear in the space-time correlation functions have been computed exactly in the limit of long wavelengths.     

Ergodic properties and thermodynamic behavior of elementary reversible cellular automata. I. Basic properties

This is the first part of a series devoted to the study of thermodynamic behavior of large dynamical systems with the use of a family of fully-discrete and conservative models named elementary reversible cellular automata (ERCAs). In this paper, basic properties such as conservation laws and phase space structure are investigated in preparation for the later studies. ERCAs are a family of one-dimensional reversible cellular automata having two Boolean variables on each site. Reflection and Boolean conjugation symmetries divide them into 88 equivalence classes. For each rule, additive conserved quantities written in a certain form are regarded as a kind of energy, if they exist. By the aid of the discreteness of the variables, every ERCA satisfies the Liouville theorem or the preservation of phase space volume. Thus, if an energy exists in the above sense, statistical mechanics of the model can formally be constructed. If a locally defined quantity is conserved, however, it prevents the realization of statistical mechanics. The existence of such a quantity is examined for each class and a number of rules which have at least one energy but no local conservation laws are selected as hopeful candidates for the realization of thermodynamic behavior. In addition, the phase space structure of ERCAs is analyzed by enumerating cycles exactly in the phase space for systems of comparatively small sizes. As a result, it is revealed that a finite ERCA is not ergodic, that is, a large number of orbits coexist on an energy surface. It is argued that this fact does not necessarily mean the failure of thermodynamic behavior on the basis of an analogy with the ergodic nature of infinite systems.