Potential-relaxation method kinetic theory

Potential-relaxation method, 38 27, 34-37 H adsorption, 38 71,75-76 kinetic theory, 38 37-41... 

After the formulation of defect thermodynamics, it is necessary to understand the nature of rate constants and transport coefficients in order to make practical use of irreversible thermodynamics in solid state kinetics. Even the individual jump of a vacancy is a complicated many-body problem involving, in principle, the lattice dynamics of the whole crystal and the coupling with the motion of all other atomic structure elements. Predictions can be made by simulations, but the relevant methods (e.g., molecular dynamics, MD, calculations) can still be applied only in very simple situations. What are the limits of linear transport theory and under what conditions do the (local) rate constants and transport coefficients cease to be functions of state When do they begin to depend not only on local thermodynamic parameters, but on driving forces (potential gradients) as well Various relaxation processes give the answer to these questions and are treated in depth later. 

We shall now almost exclusively concentrate on the fractal time random walk excluding inertial effects and the discrete orientation model of dielectric relaxation. We shall demonstrate how in the diffusion limit this walk will yield a fractional generalization of the Debye-Frohlich model. Just as in the conventional Debye relaxation, a fractional generalization of the Debye-Frohlich model may be derived from a number of very different models of the relaxation process (compare the approach of Refs. 22, 23, 28 and 34—36). The advantage of using an approach based on a kinetic equation such as the fractional Fokker-Planck equation (FFPE) however is that such a method may easily be extended to include the effects of the inertia of the dipoles, external potentials, and so on. Moreover, the FFPE (by use of a theorem of operational calculus generalized to fractional exponents and continued fraction methods) clearly indicates how many existing results of the classical theory of the Brownian motion may be extended to include fractional dynamics. 

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