Nonequilibrium statistical mechanics coefficients

The present theory can be placed in some sort of perspective by dividing the nonequilibrium field into thermodynamics and statistical mechanics. As will become clearer later, the division between the two is fuzzy, but for the present purposes nonequilibrium thermodynamics will be considered that phenomenological theory that takes the existence of the transport coefficients and laws as axiomatic. Nonequilibrium statistical mechanics will be taken to be that field that deals with molecular-level (i.e., phase space) quantities such as probabilities and time correlation functions. The probability, fluctuations, and evolution of macrostates belong to the overlap of the two fields. 

The plan of this chapter is the following. Section II gives a summary of the phenomenology of irreversible processes and set up the stage for the results of nonequilibrium statistical mechanics to follow. In Section III, it is explained that time asymmetry is compatible with microreversibility. In Section IV, the concept of Pollicott-Ruelle resonance is presented and shown to break the time-reversal symmetry in the statistical description of the time evolution of nonequilibrium relaxation toward the state of thermodynamic equilibrium. This concept is applied in Section V to the construction of the hydrodynamic modes of diffusion at the microscopic level of description in the phase space of Newton s equations. This framework allows us to derive ab initio entropy production as shown in Section VI. In Section VII, the concept of Pollicott-Ruelle resonance is also used to obtain the different transport coefficients, as well as the rates of various kinetic processes in the framework of the escape-rate theory. The time asymmetry in the dynamical randomness of nonequilibrium systems and the fluctuation theorem for the currents are presented in Section VIII. Conclusions and perspectives in biology are discussed in Section IX. 

Historically, one of the central research areas in physical chemistry has been the study of transport phenomena in electrolyte solutions. A triumph of nonequilibrium statistical mechanics has been the Debye—Hiickel—Onsager—Falkenhagen theory, where ions are treated as Brownian particles in a continuum dielectric solvent interacting through Cou-lombic forces. Because the ions are under continuous motion, the frictional force on a given ion is proportional to its velocity. The proportionality constant is the friction coefficient and has been intensely studied, both experimentally and theoretically, for almost 100... 

An alternate approach has been attempted for describing the transport phenomena in dense gas and liquid systems by means of the methods of nonequilibrium statistical mechanics, as developed by Kirkwood (K7, K8) and by Born and Green (B18, G10). Although considerable progress has been made in the development of a formal theory, the method does not at the present time provide a means for the practical calculation of the transport coefficients. Hence in this section we discuss only the applications based on Enskog s theory. 

Whereas mutual diffusion characterizes a system with a single diffusion coefficient, self-diffusion gives different diffusion coefficients for all the particles in the system. Self-diffusion thereby provides a more detailed description of the single chemical species. This is the molecular point of view [7], which makes the selfdiffusion more significant than that of the mutual diffusion. In contrast, in practice, mutual diffusion, which involves the transport of matter in many physical and chemical processes, is far more important than self-diffusion. Moreover mutual diffusion is cooperative by nature, and its theoretical description is complicated by nonequilibrium statistical mechanics. Not surprisingly, the theoretical basis of mutual diffusion is more complex than that of self-diffusion [8]. In addition, by definition, the measurements of mutual diffusion require mixtures of liquids, while self-diffusion measurements are determinable in pure liquids. 

Equation [116] is the central result of this section and is one of the most important equations in nonequilibrium statistical mechanics. It is from this point that one makes contact with the more familiar relations relating transport coefficients to time correlation functions under the guise of the so-called Green-Kubo formulas.i2.39,40... 

Liquid simulation studies have been essential in assessing the applicability of various fluctuation relations to real physical systems. These are important relations in nonequilibrium statistical mechanics that are valid far from equilibrium and can be used to derive Green-Kubo relations for transport coefficients.223,224 They show how thermodynamic irreversibility emerges from... 

Transport coefficients describe the process of relaxation to equilibrium fix)m a state perturbed by application of temperature, pressure, density, velocity or composition gradients. The theoretical description of these phenomena constitutes that part of nonequilibrium statistical mechanics that is known as the kinetic theory. The ultimate purpose of this theory is to relate the macroscopic (observable) properties of a system to the microscopic properties of the individual molecules and their interaction potentials. 

Paddison and Paul studied the diffusion of protons in fully hydrated Nafion (> =22.5) with nonequilibrium statistical mechanical transport model. The model calculated a diffusion coefficient for a proton moving along the pore center of 1.92x10" cmVs. Within 4A of the pore center proton transfer via the Grotthuss mechanism, while within 8A of the wall of the pore, the transport of the proton is predominantly vehicular in nature. 

The main problem of elementary chemical reaction dynamics is to find the rate constant of the transition in the reaction complex interacting with its environment. This problem, in principle, is close to the general problem of statistical mechanics of irreversible processes (see, e.g., Blum [1981], Kubo et al. [1985]) about the relaxation of initially nonequilibrium state of a particle in the presence of a reservoir (heat bath). If the particle is coupled to the reservoir weakly enough, then the properties of the latter are fully determined by the spectral characteristics of its susceptibility coefficients. 

No attempt will be made here to extend our results beyond the simple lowest-order limiting laws the often ad hoc modifications of these laws to higher concentrations are discussed in many excellent books,8 11 14 but we shall not try to justify them here. As a matter of fact, for equilibrium as well as for nonequilibrium properties, the rigorous extension of the microscopic calculation beyond the first term seems outside the present power of statistical mechanics, because of the rather formidable mathematical difficulties which arise. The main interests of a microscopic theory lie both in the justification qf the assumptions which are involved in the phenomenological approach and in the possibility of extending the mathematical techniques to other problems where a microscopic approach seems necessary in the particular case of the limiting laws, obvious extensions are in the direction of other transport coefficients of electrolytes (viscosity, thermal conductivity, questions involving polyelectrolytes) and of plasma physics, as well as of quantum phenomena where similar effects may be expected (conductivity of metals and semi-... 

For a gas mixture at rest, the velocity distribution function is given by the Maxwell-Boltzmann distribution function obtained from an equilibrium statistical mechanism. For nonequilibrium systems in the vicinity of equilibrium, the Maxwell-Boltzmann distribution function is multiplied by a correction factor, and the transport equations are represented as a linear function of forces, such as the concentration, velocity, and temperature gradients. Transport equations yield the flows representing the molecular transport of momentum, energy, and mass with the transport coefficients of the kinematic viscosity, v, the thermal diffirsivity, a, and Fick s diffusivity, Dip respectively. 

Denbigh 2 Drickamer and collaborators/ Wirtz, Wirtz and Hiby/ and Prigogine and co-workers have written numerous papers containing molecular interpretations of the heat of transport and the related Soret coefficient in liquids. These have proceeded on the basis of special assumptions concerning the molecular structure of the liquid and the mechanism of the diffusion process, and have assumed the validity of the equilibrium statisticaL mechanical distribution in the nonequilibrium case. In the present paper we remove the special assumptions and show from general statistical mechanics that the heat of transport consists not only of an equilibrium term but also a term which arises from the nonequilibrium perturbation to the distribution function. In the special case of a regular solution, the expression for the equilibrium... 

The first systematic attempts to calculate the viscosity and thermal conductivity of dense liquids evaluated the Green-Kubo (G-K) equations, and the Einstein relations for diffusion. The G-K expressions relate the numerical values of linear nonequilibrium transport coefficients to the relaxation of appropriate fluctuations in the equilibrium state (see Section 9.2). These studies of about 20 years ago were most important in that they gave a quantitative insight into the behavior of nonequilibrium systems and opened the door to the modem view of statistical mechanics (Hansen MacDonald 1986 McQuarrie 1976 Egelstaff 1992). From the practical standpoint, however,... 

There are numerous more advanced theories of transport coefficients in liquids, mostly based on nonequilibrium classical statistical mechanics. Some are based on approximate representations of the time-dependent reduced distribution function and others are based on the analysis of time correlation functions, which are ensemble averages of the product of a quantity evaluated at time 0 and the same quantity or a different quantity evaluated at time t For example, the self-diffusion coefficient of a monatomic liquid is given by " ... 

The goal of extending classical thermostatics to irreversible problems with reference to the rates of the physical processes is as old as thermodynamics itself. This task has been attempted at different levels. Description of nonequilibrium systems at the hydrodynamic level provides essentially a macroscopic picture. Thus, these approaches are unable to predict thermophysical constants from the properties of individual particles in fact, these theories must be provided with the transport coefficients in order to be implemented. Microscopic kinetic theories beginning with the Boltzmann equation attempt to explain the observed macroscopic properties in terms of the dynamics of simplified particles (typically hard spheres). For higher densities kinetic theories acquire enormous complexity which largely restricts them to only qualitative and approximate results. For realistic cases one must turn to atomistic computer simulations. This is particularly useful for complicated molecular systems such as polymer melts where there is little hope that simple statistical mechanical theories can provide accurate, quantitative descriptions of their behavior. 

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