On a kinetic justification of the generalized nonequilibrium thermodynamics of multicomponent systems

The problem of the kinetic justification of the generalized thermodynamics of nonequilibrium processes using the method of moments for solving the kinetic equation for a multicomponent gas mixture is examined. Generalized expressions are obtained for the entropy density, entropy flux density, and entropy production as functions of an arbitrary number of state variables (moments of the distribution function). Different variants of writing the relations between fluxes and thermodynamic forces are considered, which correspond to the Onsager version for spatially homogeneous systems and, in a more general case, lead to the generalized thermodynamic forces of a complicated form, including derivatives of the fluxes with respect to time and spatial coordinates. Some consequences and new physical effects, following from the obtained equations, are analyzed. It is shown that a transition from results of the method of moments to expressions for the entropy production and the corresponding phenomenological relations of the generalized nonequilibrium thermodynamics is possible on the level of a linearized Barnett approximation of the Chapman–Enskog method.     

Detection of multi-spin interaction of a quenched XY chain by the average work and the relative entropy

We investigate the nonequilibrium thermodynamics of a quenched XY spin chain with multi-spin interaction in a transverse field. The analytical expressions of both the average work and the relative entropy are obtained under different quenching parameters. The influences of the system parameters on the nonequilibrium thermodynamics are investigated.We find that at finite temperature the critical phenomenon induced by the multi-spin interaction and the external field can be revealed by the properties of the system nonequilibrium thermodynamics. In addition, our results indicate that the average work and the relative entropy can be used to detect both the existence and strength of the multi-spin interaction in the nonequlibrium system.     

Analysis of the conditions for ultradeep penetration of powder particles into a metallic matrix

The critical conditions for ultradeep penetration of particles when a flux of high velocity particles interacts with a matrix material are examined from the standpoint of nonequilibrium thermodynamics. The problem of the change in entropy consistent with their deformation during loading is solved qualitatively for the example of aluminum and copper samples. It is shown that ultradeep penetration of particles is a system process of mass and energy transfer owing to a developed instability in the material caused by the shock-wave action of the particle flux. The degree of disequilibrium of the process is described by the dependence of the change in entropy on the deformation of the matrix material. It turns out that the ultradeep particle penetration process occurs only in a region lying beyond a bifurcation point. Zh. Tekh. Fiz. 68, 124–125 (July 1998)     

Entropy production in open volume-preserving systems

We describe a mechanism leading to positive entropy production in volume-preserving systems under nonequilibrium conditions. We consider volume-preserving systems sustaining a diffusion process like the multibaker map or the Lorentz gas. A continuous flux of particles is imposed across the system resulting in a steady gradient of concentration. In the limit where such flux boundary conditions are imposed at arbitrarily separated boundaries for a fixed gradient, the invariant measure becomes singular. For instance, in the multibaker map, the limit invariant measure has a cumulative function given in terms of the nondifferentiable Takagi function. Because of this singularity of the invariant measure, the entropy must be defined as a coarse-grained entropy instead of the fined-grained Gibbs entropy, which would require the existence of a regular measure with a density. The coarse-grained entropy production is then shown to be asymptotically positive and, moreover, given by the entropy production expected from irreversible thermodynamics.     

Time Evolution in Macroscopic Systems. II. The Entropy

The concept of entropy in nonequilibrium macroscopic systems is investigated in the light of an extended equation of motion for the density matrix obtained in a previous study. It is found that a time-dependent information entropy can be defined unambiguously, but it is the time derivative or entropy production that governs ongoing processes in these systems. The differences in physical interpretation and thermodynamic role of entropy in equilibrium and nonequilibrium systems is emphasized and the observable aspects of entropy production are noted. A basis for nonequilibrium thermodynamics is also outlined.     

Irreversible thermodynamics of fluids

Irreversible thermodynamics of fluids is formulated based on a set of postulates. The theory thus constructed generalizes thermostatics and linear irreversible thermodynamics into the realm of nonlinear irreversible processes. In this theory the extended Gibbs relation and the entropy balance equation appear as a pair of mutually consistent equations under the postulates made. An equivalent theory is also formulated by replacing one of the postulates with another that is basically a variational principle. The variational principle yields the evolution equations for fluxes as the Euler equations that extremize the variational functional postulated. The local form of the extremized variational functional is the entropy balance equation for the irreversible processes in the system. Some further consequences of the theory are also considered. For example, nonequilibrium specific heats are shown to be at least quadratic functions of fluxes and reduce to the equilibrium specific heats in the limit of vanishing fluxes. In order to illustrate an example of possible applications, we have considered nonlinear transport processes in fluids. The connections of the present theory with other theories are discussed.     

Generalization of the Gibbsian relation for dilute systems

The Gibbsian relation is of fundamental importance to the thermodynamics of nonequilibrium systems. In this paper, we shall present an analytical derivation and several generalizations of this relation for dilute, nonequilibrium and certain highly nonequilibrium, systems. Our analysis will beindependent of the collision dynamics, because it will be based on the general kinetic equation witharbitrary collision integrals. Consequently, our analysis can provide athermodynamic derivation and several generalizations of the Gibbsian relation. Our distribution functions can also admit some arbitrary, nonequilibrium and highly nonequilibrium, forms. With the help of the generalized Gibbsian relation and a fundamental axiom to be postulated, the entropy production rates and the generalized forces and fluxes will be studied for our highly nonequilibrium systems. The second law of thermodynamics will be postulated and verified in specific cases. Onsager's reciprocity relations will be discussed.     

Generalized Fokker–Planck equations derived from generalized linear nonequilibrium thermodynamics

Recently, Compte and Jou derived nonlinear diffusion equations by applying the principles of linear nonequilibrium thermodynamics to the generalized nonextensive entropy proposed by Tsallis. In line with this study, stochastic processes in isolated and closed systems characterized by arbitrary generalized entropies are considered and evolution equations for the process probability densities are derived. It is shown that linear nonequilibrium thermodynamics based on generalized entropies naturally leads to generalized Fokker–Planck equations.     

The time derivative of information gain as excess entropy production

An information gain depending on two nonequilibrium coarse-grained statistical operators is discussed. The relation between the time derivative of information gain and excess entropy production is derived. Prigogine's stability criterion is expressed by means of the information gain. It is shown in the domain of linear nonequilibrium thermodynamics that zero time derivative of information gain corresponds to a minimum of entropy production and K theorem can be formulated.     

Entropy production, fractals, and relaxation to equilibrium

The theory of entropy production in nonequilibrium, Hamiltonian systems, previously described for steady states using partitions of phase space, is here extended to time dependent systems relaxing to equilibrium. We illustrate the main ideas by using a simple multibaker model, with some nonequilibrium initial state, and we study its progress toward equilibrium. The central results are (i) the entropy production is governed by an underlying, exponentially decaying fractal structure in phase space, (ii) the rate of entropy production is largely independent of the scale of resolution used in the partitions, and (iii) the rate of entropy production is in agreement with the predictions of nonequilibrium thermodynamics.     

Generalization of the second law for a transition between nonequilibrium states

The maximum work formulation of the second law of thermodynamics is generalized for a transition between nonequilibrium states. The relative entropy, the Kullback-Leibler divergence between the nonequilibrium states and the canonical distribution, determines the maximum ability to work. The difference between the final and the initial relative entropies with an effective temperature gives the maximum dissipative work for both adiabatic and isothermal processes. Our formulation reduces to both the Vaikuntanathan-Jarzynski relation and the nonequilibrium Clausius relation in certain situations. By applying our formulation to a heat engine the Carnot cycle is generalized to a circulation among nonequilibrium states.     

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.     

Comments on the Entropy of Nonequilibrium Steady States

We discuss the entropy of nonequilibrium steady states. We analyze the so-called spontaneous production of entropy in certain reversible deterministic nonequilibrium system, and its link with the collapse of such systems towards an attractor that is of lower dimension than the dimension of phase space. This means that in the steady state limit, the Gibbs entropy diverges to negative infinity. We argue that if the Gibbs entropy is expanded in a series involving 1, 2,... body terms, the divergence of the Gibbs entropy is manifest only in terms involving integrals whose dimension is higher than, approximately, the Kaplan–Yorke dimension of the steady state attractor. All the low order terms are finite and sum in the weak field limit to the local equilibrium entropy of linear irreversible thermodynamics.     

Maximum entropy production principle in physics,chemistry and biology

The tendency of the entropy to a maximum as an isolated system is relaxed to the equilibrium (the second law of thermodynamics) has been known since the mid-19th century. However, independent theoretical and applied studies, which suggested the maximization of the entropy production during nonequilibrium processes (the so-called maximum entropy production principle, MEPP), appeared in the 20th century. Publications on this topic were fragmented and different research teams, which were concerned with this principle, were unaware of studies performed by other scientists. As a result, the recognition and the use of MEPP by a wider circle of researchers were considerably delayed. The objectives of the present review consist in summation and analysis of studies dealing with MEPP. The first part of the review is concerned with the thermodynamic and statistical basis of the principle (including the relationship of MEPP with the second law of thermodynamics and Prigogine's principle). Various existing applications of the principle to analysis of nonequilibrium systems will be discussed in the second part.     

Fluctuation theorem and chaos

The heat theorem (i.e. the second law of thermodynamics or the existence of entropy) is a manifestation of a general property of hamiltonian mechanics and of the ergodic hypothesis. In nonequilibrium thermodynamics of stationary states the chaotic hypothesis plays a similar role: it allows a unique determination of the probability distribution (called SRB distribution) on phase space providing the time averages of the observables. It also implies an expression for a few averages concrete enough to derive consequences of symmetry properties like the fluctuation theorem or to formulate a theory of coarse graining unifying the foundations of equilibrium and of nonequilibrium.     

Reversibility, heat dissipation, and the importance of the thermal environment in stochastic models of nonequilibrium steady states

We examine stochastic processes that are used to model nonequilibrium processes (e.g., pulling RNA or dragging colloids) and so deliberately violate detailed balance. We argue that by combining an information-theoretic measure of irreversibility with nonequilibrium work theorems, the thermal physics implied by abstract dynamics can be determined. This measure is bounded above by thermodynamic entropy production and so may quantify how well a stochastic dynamics models reality. We also use our findings to critique various modeling approaches and notions arising in steady-state thermodynamics.     

Quantum corrections to the entropy in a driven quantum Brownian motion model

The quantum Brownian motion model is a typical model in the study of nonequilibrium quantum thermodynamics. Entropy is one of the most fundamental physical concepts in thermodynamics.In this work, by solving the quantum Langevin equation, we study the von Neumann entropy of a particle undergoing quantum Brownian motion. We obtain the analytical expression of the time evolution of the Wigner function in terms of the initial Wigner function. The result is applied to the thermodynamic equilibrium initial state, which reproduces its classical counterpart in the high temperature limit. Based on these results, for those initial states having well-defined classical counterparts, we obtain the explicit expression of the quantum corrections to the entropy in the weak coupling limit. Moreover, we find that for the thermodynamic equilibrium initial state, all terms odd in h are exactly zero. Our results bring important insights to the understanding of entropy in open quantum systems.