Statistical-Mechanical Foundations for a Generalized Thermodynamics of Dissipative Processes

A statistical-mechanical formalism for nonequilibrium systems, namely the nonequilibrium statistical operator method, provides microscopic foundations for a generalized thermodynamics of dissipative processes. This formalism is based on a unifying variational approach that is considered to be encompassed in Jaynes' Predictive Statistical Mechanics and principle of maximization of the statistical-informational entropy. Within the framework of the statistical thermodynamics that follows from the method, we demonstrate the existence of generalized forms of the theorem of minimum (informational) entropy production, the criterion for evolution, and the thermodynamic (in)stability criterion. The formalism is not restricted to local equilibrium but, in principle, to general conditions (its complete domain of validity is not yet fully determined). A H-theorem associated to the formalism is presented in the form of an increase of the informational entropy along the evolution of the system. Some of the results are illustrated in an application to the study of a model for a photoexcited direct-gap semiconductor.     

A Variational Principle for Thermodynamical Waves

When the dissipative processes are dominant in the system, the assumption of local equilibrium holds good and the space time evolution of irreversible system can be described by the variational principle of GYARMATI. However when imposed changes in the state variables are fast, the system can not be in a state of local equilibrium and to define the nonequilibrium state of the system it is necessary to extend the formalism of classical irreversible thermodynamics. The wave approach of Onsagerian thermodynamics is one such pursuit and is a direct generalization of the original Onsager-Machlup proposition. An important consequence of this theory is that it leads to transport equations with finite propagation velocities, which are referred to as thermodynamical waves. In this note we endeavour to write the appropriate form of GYARMATI'S variational principle for thermodynamical waves.     

General H-Theorem for Hard Spheres

The maximum entropy formalism is used to investigate the growth of entropy (H-theorem) for an isolated system of hard spheres in an external potential under general boundary geometry. Assuming that only correlations of a finite number of particles are controlled and the rest maximizes entropy, we obtain an H-theorem for such a system The limiting cases such as the modified Enskog equation and linear kinetic theory are discussed.     

The Boltzmann equation from quantum field theory

We show from first principles the emergence of classical Boltzmann equations from relativistic nonequilibrium quantum field theory as described by the Kadanoff–Baym equations. Our method applies to a generic quantum field, coupled to a collection of background fields and sources, in a homogeneous and isotropic spacetime. The analysis is based on analytical solutions to the full Kadanoff–Baym equations, using the WKB approximation. This is in contrast to previous derivations of kinetic equations that rely on similar physical assumptions, but obtain approximate equations of motion from a gradient expansion in momentum space. We show that the system follows a generalized Boltzmann equation whenever the WKB approximation holds. The generalized Boltzmann equation, which includes off-shell transport, is valid far from equilibrium and in a time dependent background, such as the expanding universe.     

Time-dependent statistics of binary linear lattices

The time-dependent statistics of binary linear lattices is investigated on the basis of a master equation at the microscopic level. It is assumed that the kinetics may be formulated as transformations of specified sequences of clusters ofA units andB units into other specified sequences. On the basis of aStosszahlansatz, a master equation at the macroscopic level is derived. In the limit of a large system, the densities of clusters of all types satisfy rate equations similar to the equations of chemical kinetics. AnH-theorem is proven and the nonequilibrium thermodynamics of the system is studied. The theory has application to the kinetics of the helix-coil phase transition in biopolymers.     

Irreversibility in the hard-spheres gas: H theorem and the Gibbs relation

An H-functional is suggested in terms of the single-particle distribution function governed by the Enskog kinetic equation. It is shown to be restricted to situations near the local equilibrium state. A generalized H-theorem valid for all initial situations is established from the point of view of a master equation for the hard-spheres gas. The thermodynamics of irreversible processes is then discussed in relation to the basic foundations of the kinetic theory of dense gases.     

Derivation of the nonlinear hydrodynamic equations using multi-mode techniques

A general mode-mode coupling theory is developed for the microscopic mass, energy and momentum densities of a simple classical fluid. A projection operator method is employed to derive a generalized Langevin equation that contains nonlinearities of all orders with both convective and dissipative terms. A general nonequilibrium ensemble average, which contains local equilibrium as a special case, is employed to derive nonlinear transport equations that are nonlocal in both space and time.The nonlinear Euler and Navier-Stokes equations are recovered using a factorization procedure based on an inverse system size approximation. We show that in the context of mode-mode coupling theory, nonlinearities of all orders must be retained to derive the full nonlinear transport equations. We also slow that the space and time dependent nonequilibrium pressure and transport coefficients are functions of the nonequilibrium mass and internal energy densities. The thermodynamic closure relationships follow as a natural consequence of mode-mode coupling theory. For a system linearly displaced from equilibrium we demonstrate the role of the corrections to our factorization approximation in renormalizing the transport coefficients.     

On the hydrodynamic theory of a magnetic liquid I. General description

Using Zubarev's method of nonequilibrium statistical operator, the generalized hydrodynamic equations are obtained for a model of magnetic liquid in an inhomogeneous external field. In this model the “liquid” subsystem is treated as a classical one and the “magnetic” subsystem is described by quantum mechanical methods. The properties of the transport equations are analysed in the case of a weak nonequilibrium. The equations for time correlation functions and collective mode spectrum are also found in the same manner. It is shown that the generalized hydrodynamic equations reduce to the well-known results in the limiting cases when the dynamic variables of one subsystem are formally neglected. As an illustration, a simple model of spin relaxation is considered, and the frequency matrix and the matrix of memory functions are calculated. A comparison with previous works is made.     

Lagrangean and Hamiltonian fractional sequential mechanics

The models described by fractional order derivatives of Riemann-Liouville type in sequential form are discussed in Lagrangean and Hamiltonian formalism. The Euler-Lagrange equations are derived using the minimum action principle. Then the methods of generalized mechanics are applied to obtain the Hamilton’s equations. As an example free motion in fractional picture is studied. The respective fractional differential equations are explicitly solved and it is shown that the limitα→1⁺ recovers classical model with linear trajectories and constant velocity. Presented at the 11th Colloquium “Quantum Groups and Integrable Systems”, Prague, 20–22 June 2002.     

A perturbative nonequilibrium renormalization group method for dissipative quantum mechanics

We study a generic problem of dissipative quantum mechanics, a small local quantum system with discrete states coupled in an arbitrary way (i.e. not necessarily linear) to several infinitely large particle or heat reservoirs. For both bosonic or fermionic reservoirs we develop a quantum field-theoretical diagrammatic formulation in Liouville space by expanding systematically in the reservoir-system coupling and integrating out the reservoir degrees of freedom. As a result we obtain a kinetic equation for the reduced density matrix of the quantum system. Based on this formalism, we present a formally exact perturbative renormalization group (RG) method from which the kernel of this kinetic equation can be calculated. It is demonstrated how the nonequilibrium stationary state (induced by several reservoirs kept at different chemical potentials or temperatures), arbitrary observables such as the transport current, and the time evolution into the stationary state can be calculated. Most importantly, we show how RG equations for the relaxation and dephasing rates can be derived and how they cut off generically the RG flow of the vertices. The method is based on a previously derived real-time RG technique [1-4] but formulated here in Laplace space and generalized to arbitrary reservoir-system couplings. Furthermore, for fermionic reservoirs with flat density of states, we make use of a recently introduced cutoff scheme on the imaginary frequency axis [5] which has several technical advantages. Besides the formal set-up of the RG equations for generic problems of dissipative quantum mechanics, we demonstrate the method by applying it to the nonequilibrium isotropic Kondo model. We present a systematic way to solve the RG equations analytically in the weak-coupling limit and provide an outlook of the applicability to the strong-coupling case.     

Transition state theory: A generalization to nonequilibrium systems with power-law distributions

Transition state theory (TST) is generalized to nonequilibrium systems with power-law distributions. The stochastic dynamics that gives rise to the power-law distributions for the reaction coordinate and momentum is modeled by Langevin equations and corresponding Fokker-Planck equations. It is considered that a system far away from equilibrium does not have to relax to a thermal equilibrium state with Boltzmann-Gibbs distribution, but asymptotically approaches a nonequilibrium stationary state with a power-law distribution. Thus, we obtain a possible generalization of TST rates to nonequilibrium systems with power-law distributions. Furthermore, we derive the generalized TST rate constants for one-dimensional and n-dimensional Hamiltonian systems away from equilibrium, and obtain a generalized Arrhenius rate for systems with power-law distributions.     

Molecular derivation of the hydrodynamic equations for a binary fluid

In this paper, the hydrodynamic equations and the associated transport coefficients are derived for a simple binary fluid from molecular considerations. This is a generalization of the methods of Felderhof and Oppenheim and of Selwyn to multicomponent systems. A linear response formalism is used to describe the relaxation of the binary system from an initial nonequilibrium state. Explicit molecular expressions are given for the transport coefficients in terms of time correlation functions of generalized current densities. These densities have the useful property of not containing a conserved part. The correlation functions are then related to a set of phenomenological coefficients in the theory of nonequilibrium thermodynamics. This explicit identification enables one to relate the correlation functions to experimentally measured transport coefficients.Supported by the National Science Foundation.     

A new theory of elementary matter

This is the first of a series of articles that reviews and expands upon a new theory of elementary matter. This paper presents an exposition of the philosophical approach and its general implications. The ensuing explicit form of the mathematical expression of the theory and several applications in the atomic and elementary particle domains will be developed in the succeeding parts of this series.The theory is based on three axioms: the principle of general relativity, a generalized Mach principle, and a correspondence principle. The approach is basically a deterministic, relativistic field theory which fully incorporates the idea that any realistic physical system is in facta closed system, without separable parts. It is shown that the most primitive mathematical expression of this theory, following as anecessary consequence of its axioms, is in terms of a set of coupled nonlinear spinor field equations. Nevertheless, the exact formalism is constructed to asymptotically approach the quantum mechanical formalism for a many-particle system, in the limit of sufficiently small energy-momentum transfer among the components of the considered closed system. Thus, all of the mathematical predictions of nonrelativistic quantum mechanics are contained in this theory, as a mathematical approximation. However, predictions follow from the exact form of this theory (where energy-momentum transfer can be arbitrarily large) that are not contained in the quantum theory.     

Nonequilibrium Relaxation of Bose-Einstein Condensates: Real-Time Equations of Motion and Ward Identities

We present a field-theoretical method to obtain consistently the equations of motion for small amplitude condensate perturbations in a homogeneous Bose-condensed gas directly in real time. It is based on a linear response and combines the Schwinger-Keldysh formulation of nonequilibrium quantum field theory with the Nambu-Gor'kov formalism of quasiparticle excitations in the condensed phase and the tadpole method in quantum field theory. This method leads to causal equations of motion that allow us to study the nonequilibrium evolution as an initial value problem. It also allows us to extract directly the Ward identities, which are a consequence of the underlying gauge symmetry and which in equilibrium lead to the Hugenholtz-Pines theorem. An explicit one-loop calculation of the equations of motion beyond the Hartree-Fock-Bogoliubov approximation reveals that the nonlocal, absorptive contributions to the self-energies corresponding to the Beliaev and Landau damping processes are necessary to fulfill the Ward identities in or out of equilibrium. It is argued that a consistent implementation at low temperatures must be based on the loop expansion, which is shown to fulfill the Ward identities order by order in perturbation theory.     

A generalized Schrödinger formalism as a Hilbert space representation of a generalized Liouville equation

A generalized Schrödinger formalism has been presented which is obtained as a Hilbert space representation of a Liouville equation generalized to include the action as a dynamical variable, in addition to the positions and the momenta. This formalism applied to a classical mechanical system had been shown to yield a similar set of Schrödinger like equations for the classical dynamical system of charged particles in a magnetic field. The novel quantum-like predictions for this classical mechanical system have been experimentally demonstrated and the results are presented.     

Kinetic transport theory with quantum coherence

We derive transport equations for fermions and bosons in spatially or temporally varying backgrounds with special symmetries, by use of the Schwinger-Keldysh formalism. In a noninteracting theory the coherence information is shown to be encoded in new singular shells for the 2-point function. Imposing this phase space structure to the interacting theory leads to a a self-consistent equation of motion for a physcial density matrix, including coherence and a well defined collision integral. The method is applied e.g. to demonstrate how an initially coherent out-of-equlibrium state approaches equlibrium through decoherence and thermalization.     

Nonlinear transport in far-from-equilibrium semiconductors

Summary Using a nonlinear transport theory, derived from the nonequilibrium statistical operator method, we obtain the equations that govern the evolution of the nonequilibrium state of a highly photoexcited direct-gap polar semiconductor, and its nonequilibrium mobility coefficient. It provides an analytic method that allows for a deep physical insight into the influence of the nonequilibrium irreversible evolution of the plasma in the semiconductor on its transport properties. We demonstrate that, under quite general conditions, the strong dependence of the momentum and energy relaxation times on the irreversible evolution of the macroscopic nonequilibrium state of the system results in the existence of a structured transient mobility,i.e. one with maxima and minima, with or without overshoot. A criterion for the occurrence of this structure is derived as well as several general properties of the ultrafast transient are discussed. The authors of this paper have agreed to not receive the proofs for correction.     

Entropy Function Approach to the Lattice Boltzmann Method

In this paper, we present the construction of the Lattice Boltzmann method equipped with the H-theorem. Based on entropy functions whose local equilibria are suitable to recover the Navier–Stokes equations in the framework of the Lattice Boltzmann method, we derive a collision integral which enables simple identification of transport coefficients, and which circumvents construction of the equilibrium. We discuss performance of this approach as compared to the standard realizations.     

Response function theory for far-from-equilibrium statistical systems

A formalism to determine the response function of a sample in conditions far from thermal equilibrium is presented. It consists in a generalization of scattering theory coupled to the statistical theory of irreversible processes, the nonequilibrium statistical operator method, developed by Zubarev. The scattering cross section is expressed in terms of double-time correlation functions, which are related to appropriate nonequilibrium thermodynamic Green's functions. The latter are also used to treat generalized transport equations, and, as an illustration, the method is applied to the study of the time-resolved Raman spectroscopy of a photoexcited semiconductor plasma.