Microscopic particle transport theory

The stochastic model of ion transport in liquids emphasizes the role of fast-fluctuating forces arising from short (compared to the ion transition time), random interactions with many neighboring particles. Langevin s analysis of this model was reviewed by Buck [126] with a focus on aspects important for macroscopic transport theories, namely those based on the Nernst-Planck equation. However, from a microscopic point of view, application of the Fokker-Planck equation is more fruitful [127]. In particular, only the latter equation can account for local friction anisotropy in the interfacial region, and thereby provide a better understanding of the difference between the solution and interfacial ion transport. 

Kinetic theory is introduced and developed as the initial step toward understanding microscopic transport phenomena. It is used to develop relations for the thermal conductivity which are compared to experimental measurements for a variety of solids. Next, it is shown that if the time- or length scale of the phenomena are on the order of those for scattering, kinetic theory cannot be used but instead Boltzmann transport theory should be used. It was shown that the Boltzmann transport equation (BTE) is fundamental since it forms the basis for a vast variety of transport laws such as the Fourier law of heat conduction, Ohm s law of electrical conduction, and hyperbolic heat conduction equation. In addition, for an ensemble of particles for which the particle number is conserved, such as in molecules, electrons, holes, and so forth, the BTE forms the basis for mass, momentum, and energy conservation equa-... 

For the more microscopic approach of an MD simulation of a chain in solvent particles, it is useful to also look at the theory from a more microscopic point of view, in particular in order to assess its limitations. The derivation of equations of motion of the Smoluchowski type and the discussion of the involved errors is a standard problem in modem transport theory. In the present case, the form of the hydrodynamic interaction tensor has to be derived from the microscopies, However, analytical... 

In its more advanced aspects, kinetic theory is based upon a description of the gas in terms of the probability of a particle having certain values of coordinates and velocity, at a given time. Particle interactions are developed by the ordinary laws of mechanics, and the results of these are averaged over the probability distribution. The probability distribution function that is used for a given macroscopic physical situation is determined by means of an equation, the Boltzmann transport equation, which describes the space, velocity, and time changes of the distribution function in terms of collisions between particles. This equation is usually solved to give the distribution function in terms of certain macroscopic functions thus, the macroscopic conditions imposed upon the gas are taken into account in the probability function description of the microscopic situation. 

The macroscopic properties of a material are related intimately to the interactions between its constituent particles, be they atoms, ions, molecules, or colloids suspended in a solvent. Such relationships are fairly well understood for cases where the particles are present in low concentration and interparticle interactions occur primarily in isolated clusters (pairs, triplets, etc.). For example, the pressure of a low-density vapor can be accurately described by the virial expansion,1 whereas its transport coefficients can be estimated from kinetic theory.2,3 On the other hand, using microscopic information to predict the properties, and in particular the dynamics, of condensed phases such as liquids and solids remains a far more challenging task. In these states... 

It is extremely difficult to model macroscopic transport of mass, energy, and momentum in porous media commonly encountered in various fields of science and engineering based on microscopic transport models that account for variation of velocity and temperature as well as other quantities of interest past individual solid particles. The basic idea of porous media theory, therefore, is to volume average the quantities of interest and develop field equations based on these average quantities. 

The research of Roy Jackson combines theory and experiment in a distinctive fashion. First, the theory incorporates, in a simple manner, inertial collisions through relations based on kinetic theory, contact friction via the classical treatment of Coulomb, and, in some cases, momentum exchange with the gas. The critical feature is a conservation equation for the pseudo-thermal temperature, the microscopic variable characterizing the state of the particle phase. Second, each of the basic flows relevant to processes or laboratory tests, such as plane shear, chutes, standpipes, hoppers, and transport lines, is addressed and the flow regimes and multiple steady states arising from the nonlinearities (Fig. 6) are explored in detail. Third, the experiments are scaled to explore appropriate ranges of parameter space and observe the multiple steady states (Fig. 7). One of the more striking results is the... 

Theoretical modeling tries to give a quantitative explanation of the fines migration mechanism by means of derived mathematical formulations. The mathematical formulations take into account the dynamic interactions of the fines with other suspended particles, the solid substrate of the porous medium, and the liquid phases surrounding the particles. These microscopic theories of fines migration are intended to give insight into the release, transport, and deposition of fines. 

In many respects, at a superficial level, the theory for the chemical reaction problem is much simpler than for the velocity autocorrelation function. The simplifications arise because we are now dealing with a scalar transport phenomenon, and it is the diffusive modes of the solute molecules that are coupled. In the case of the velocity autocorrelation function, the coupling of the test particle motion to the collective fluid fields (e.g., the viscous mode) must be taken into account. At a deeper level, of course, the same effects must enter into the description of the reaction problem, and one is faced with the problem of the microscopic treatment of the correlated motion of a pair of molecules that may react. In the following sections, we attempt to clarify and expand on these parallels. 

Out of equilibrium there is no such rigorous principle. However, macroscopicaUy one can find a large variety of phenomenological equations for the time evolution which are based on macroscopic quantities alone, e.g., the diffusion equation, the heat transport equation, and the Navier-Stokes equations for hydrodynamics. A microscopic dynamical theory for the time evolution of slow variables such as the momentum density or the particle density with molecular spatial resolution is highly desirable. 

The next important advance in the theory, and the one that provided the foundation for all later work in this field, was made by Boltzmann, who in 1872 derived an equation for the time rate of change of the distribution function for a dilute gas that is not in equilibrium—the Boltzmann transport equation. (See Boltzmann and also Klein. " ) Boltzmann s equation gives a microscopic description of nonequilibrium processes in the dilute gas, and of the approach of the gas to an equilibrium state. Using the Boltzmann equation. Chapman and Enskog derived the Navier-Stokes equations and obtained expressions for the transport coefficients for a dilute gas of particles that interact with pairwise, short-range forces. Even now, more than 100 years after the derivation of the Boltzmann equation, the kinetic theory of dilute gases is largely a study of special solutions of that equation for various initial and boundary conditions and various compositions of the gas.t... 

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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