Diffusion random walk analysis

The diffusion of an impurity atom in a crystal, say K in NaCl, involves other considerations that influence diffusion. In such cases, the probability that the impurity will exchange with the vacancy will depend on factors such as the relative sizes of the impurity compared to the host atoms. In the case of ionic movement, the charge on the diffusing species will also play a part. These factors can also be included in a random-walk analysis by including jump probabilities of the host and impurity atoms and vacancies, all of which are likely to vary from one impurity to another and from one crystal structure to another. All of these alterations can be... 

Small elements lose their identity by the action of molecular diffusion, and the Einstein random walk analysis estimates this time as... 

In Sect. 2.1, the timescale over which the diffusion equation is not strictly valid was discussed. When using the molecular pair analysis with an expression for h(f) derived from a diffusion equation analysis or random walk approach, the same reservations must be borne in mind. These difficulties with the diffusion equation have been commented upon by Naqvi et al. [38], though their comments are largely within the framework of a random walk analysis and tend to miss the importance the solvent cage and velocity relaxation effects. 

Surface diffusion may be treated by a random-walk analysis. We assume that the molecular motion is completely random and that the jumps from site to site are of equal length, which is equal to the nearest-neighbor distance d. With these assumptions, the preexponential factor for diffusion is (23). 

In Sect. 3, the Noyes approach to analysing reaction rates based on the molecular pair approach is discussed [5]. Both this and the diffusion equation analysis are identical under conditions where the diffusion equation is valid and when the appropriate recombination reaction rate for a molecular pair is based on the diffusion equation. Some comments by Naqvi et al. [38] and Stevens [455] have obscured this identity. The diffusion equation is a valid approximation to molecular motion when the details of motion in a cage are no longer of importance. This time is typically a few picoseconds in a mobile liquid. When extrapolating the diffusion equation back to such times, it should be recalled that the diffusion is a continuum form of random walk [271]. While random walks can be described with both a distribution of jump frequencies and distances, nevertheless, the diffusion equation would not describe a random walk satisfactorily over times less than about five jump periods (typically 10 ps in mobile liquids). Even with a distribution of jump distances and frequencies, the random walk model of molecular motion does not represent such motion adequately well as these times (nor will the telegrapher s or Fokker-Planck equation be much better). It is therefore inappropriate to compare either the diffusion equation or random walk analysis with that of the molecular pair over such times. Finally, because of the inherent complexity of molecular motion, it is doubtful whether it can be described adequately in terms of average jump distances and frequencies. These jump characteristics are only operational terms for very complex quantities which derive from the detailed molecular motion of the liquid. For this very reason, the identification of the diffusion coefficient with a specific jump formula (e.g. D = has been avoided. 

It is in this region of time that the random walk or diffusion equation analysis is least adequate. The prime failure of the random walk analysis is to ignore the oscillatory motion of molecules. The encounter pair separates from encounter but gets reflected back towards each other by the solvent cage after a time about equal to the period of oscillations in a solvent cage. To incorporate this effect, Noyes [265] used the approximate form of h(t)... 

Direct observation of molecular diffusion is the most powerful approach to evaluate the bilayer fluidity and molecular diffusivity. Recent advances in optics and CCD devices enable us to detect and track the diffusive motion of a single molecule with an optical microscope. Usually, a fluorescent dye, gold nanoparticle, or fluorescent microsphere is used to label the target molecule in order to visualize it in the microscope [31-33]. By tracking the diffusive motion of the labeled-molecule in an artificial lipid bilayer, random Brownian motion was clearly observed (Figure 13.3) [31]. As already mentioned, the artificial lipid bilayer can be treated as a two-dimensional fluid. Thus, an analysis for a two-dimensional random walk can be applied. Each trajectory observed on the microscope is then numerically analyzed by a simple relationship between the displacement, r, and time interval, T,... 

Such a mechanism is not incompatible with a Haven ratio between 0.3 and 0.6 which is usually found for mineral glasses (Haven and Verkerk, 1965 Terai and Hayami, 1975 Lim and Day, 1978). The Haven ratio, that is the ratio of the tracer diffusion coefficient D determined by radioactive tracer methods to D, the diffusion coefficient obtained from conductivity via the Nernst-Einstein relationship (defined in Chapter 3) can be measured with great accuracy. The simultaneous measurement of D and D by analysis of the diffusion profile obtained under an electrical field (Kant, Kaps and Offermann, 1988) allows the Haven ratio to be determined with an accuracy better than 5%. From random walk theory of ion hopping the conductivity diffusion coefficient D = (e /isotropic medium. Hence for an indirect interstitial mechanism, the corresponding mobility is expressed by... 

In order to calculate the density of reactant B about A, it is necessary to know by what means the reactants migrate in solution. Under most circumstances, diffusion is a very adequate description (the limitations of and complications to diffusion are discussed in Sect. 6, Chap. 8 Sect. 2 and Chap. 11). In this simple analysis of diffusion, Fick s laws will be used with little further justification, save to note that Fick s second law is identical to the equation satisfied by a random walk function. Hardly a surprising result, because diffusion is a random walk with no retention of information about where the diffusing species was before its current location. In Chap. 3 Sect. 1, the diffusion equation is derived from thermodynamic considerations and the continuity equation (law of conservation of mass). 

By contrast, when both the reactive solute molecules are of a size similar to or smaller than the solvent molecules, reaction cannot be described satisfactorily by Langevin, Fokker—Planck or diffusion equation analysis. Recently, theories of chemical reaction in solution have been developed by several groups. Those of Kapral and co-workers [37, 285, 286] use the kinetic theory of liquids to treat solute and solvent molecules as hard spheres, but on an equal basis (see Chap. 12). While this approach in its simplest approximation leads to an identical result to that of Smoluchowski, it is relatively straightforward to include more details of molecular motion. Furthermore, re-encounter events can be discussed very much more satisfactorily because the motion of both reactants and also the surrounding solvent is followed. An unreactive collision between reactant molecules necessarily leads to a correlation in the motion of both reactants. Even after collision with solvent molecules, some correlation of motion between reactants remains. Subsequent encounters between reactants are more or less probable than predicted by a random walk model (loss of correlation on each jump) and so reaction rates may be expected to depart from those predicted by the Smoluchowski analysis. Furthermore, such analysis based on the kinetic theory of liquids leads to both an easy incorporation of competitive effects (see Sect. 2.3 and Chap. 9, Sect. 5) and back reaction (see Sect. 3.3). Cukier et al. have found that to include hydrodynamic repulsion in a kinetic theory analysis is a much more difficult task [454]. 

The microscopic view of diffusion starts with the movements of individual ions. Ions dart about haphazardly, executing a random walk. By an analysis of one-dimensional random walk, a simple law can be derived (see Section 4.2.6) for the mean square distance-cc traversedby an ionin atimef. This is theEinstein-Smoluchowski equation... 

In seeking an atomic view of the process of conduction, one approach is to begin with the picture of ionic movements as described in the treatment of diffusion (Section 4.2.4) and then to consider how these movements are perturbed by an electric field. In the treatment of ionic movements, it was stated that the ions in solution perform a random walk in which all possible directions are equally likely for any particular step. The analysis of such a random walk indicated that the mean displacement of ions is zero (Section 4.2.4), diffusion being the result of the statistical bias in the movement of ions, due to inequalities in their numbers in different regions. 

Note that this solution yields exactly the same physics arrived at in eqn (7.11) as a result of our analysis of the random walk. In addition, the correspondence between the diffusion constant D and the jump rate F also becomes evident. 

The random walk approach is based on the random-walk concept, which was originally apphed to the problem of diffusion and later adopted by Flory [3] to deduce the conformations of macromolecules in solution. The earliest analysis was by Simha et al. [4], who neglected volume effects and treated the polymer as a random walk. Basically, the solution was represented by a three-dimensional lattice. 

The section begins with the random walk, a useful model from statistical physics that provides insight into the kinetics of molecular diffusion. From this starting point, the fundamental relationship between diffusive flux and solute concentration. Pick s law, is described and used to develop general mass-conservation equations. These conservation equations are essential for analysis of rates of solute transport in tissues. 

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