Distribution functions relaxation

We are going to carry out some spatial integrations here. We suppose that tire distribution function vanishes at the surface of the container and that there is no flow of energy or momentum into or out of the container. (We mention in passing that it is possible to relax this latter condition and thereby obtain a more general fonn of the second law than we discuss here. This requires a carefiil analysis of the wall-collision temi The interested reader is referred to the article by Dorfman and van Beijeren [14]. Here, we will drop the wall operator since for the purposes of this discussion it merely ensures tliat the distribution fiinction vanishes at the surface of the container.) The first temi can be written as... 

In principle, the relaxation spectrum H(r) describes the distribution of relaxation times which characterizes a sample. If such a distribution function can be determined from one type of deformation experiment, it can be used to evaluate the modulus or compliance in experiments involving other modes of deformation. In this sense it embodies the key features of the viscoelastic response of a spectrum. Methods for finding a function H(r) which is compatible with experimental results are discussed in Ferry s Viscoelastic Properties of Polymers. In Sec. 3.12 we shall see how a molecular model for viscoelasticity can be used as a source of information concerning the relaxation spectrum. 

It should be observed that Eq. (3.102) may be viewed as a distribution function for relaxation times. In fact, if N,. is large enougli, integer increments in p may be approximated as continuous p values. This makes Tp continuous also. The significance of this is that Eq.(3.90) can be written as an integral in analogy with (3.62) if p is continuous ... 

A gas is not in equilibrium when its distribution function differs from the Maxwell-Boltzman distribution. On the other hand, it can also be shown that if a system possesses a slight spatial nonuniformity and is not in equilibrium, then the distribution function will monotonically relax in velocity space to a local Maxwell-Boltzman distribution, or to a distribution where p = N/V, v and temperature T all show a spatial dependence [bal75]. 

G. J. Hirasaki 2003, (Diffusion-relaxation distribution functions of sedimentary rocks in different saturation states), Magn. Reson. Imaging 21, 305-310. 

In Section 4.1.4.1, we develop the estimation of the relaxation distribution functions from NMR data. These are used to determine porosity and saturation distributions. In Section 4.1.4.2, we develop the estimation of permeability distri-... 

One may also show that MPC dynamics satisfies an H theorem and that any initial velocity distribution will relax to the Maxwell-Boltzmann distribution [11]. Figure 2 shows simulation results for the velocity distribution function that confirm this result. In the simulation, the particles were initially uniformly distributed in the volume and had the same speed v = 1 but different random directions. After a relatively short transient the distribution function adopts the Maxwell-Boltzmann form shown in the figure. 

Mw = 2.1 x 106g/mol) in water, which is denoted Cw(t) in the original work [44]. The subscript indicates that both the incoming beam and the scattered light are vertically polarized. The correlation function was recorded for a solution with a concentration of c = 0.005 g/L at a scattering vector of q = 8.31 x 106m-1. The inset shows the distribution function of the relaxation times determined by an inverse Laplace transformation. 

The inset shows a unimodal distribution of relaxation times r = I 1 obtained by a CONTIN analysis. Besides CONTIN there is a number of alternative techniques [51] for the determination of the distribution from the correlation function. Detailed discussions of this topic have been given by Stock and Ray [52] and by Stepanek [50]. 

Distributions of relaxation or retardation times are useful and important both theoretically and practicably, because // can be calculated from /.. (and vice versa) and because from such distributions other types of viscoelastic properties can be calculated. For example, dynamic modulus data can be calculated from experimentally measured stress relaxation data via the resulting // spectrum, or H can be inverted to L, from which creep can be calculated. Alternatively, rather than going from one measured property function to the spectrum to a desired property function [e.g., Eft) — // In Schwarzl has presented a series of easy-to-use approximate equations, including estimated error limits, for converting from one property function to another (11). 

In the linearized LB equation Eq. (7), the ensemble averaged effect of the particle-particle collision is now represented by a relaxation of the distribution function ft to the equilibrium function /fq, where the matrix Ly does not necessarily have to correspond to an existing set of collision rules. The question now arises if L can be simplified even further to the form Ly = aSy, so that the LB equation takes the form (with x — -St/a)... 

It can not be described by means of a single Debye process, but more complicated relaxation functions involving distributions of relaxation times (like the Cole-Cole function [117]) or distributions of energy barriers (like log-normal functions [118]) have to be used for its description. Usually a narrowing of the relaxation function with increasing temperature is observed. The Arrhenius temperature dependence of the associated characteristic time is ... 

The elastic contribution is also called elastic incoherent structure factor (EISF). It may be interpreted as the Fourier transformed of the asymptotic distribution of the hopping atom for infinite times. In an analogous way to the relaxation functions (Eq. 4.6 and Eq. 4.7), the complete scattering function is obtained by averaging Eq. 4.22 with the barrier distribution function g E) obtained, e.g. by dielectric spectroscopy (Eq. 4.5)... 

An important theoretical development for the outer-sphere relaxation was proposed in the 1970s by Hwang and Freed (138). The authors corrected some earlier mistakes in the treatment of the boundary conditions in the diffusion equation and allowed for the role of intermolecular forces, as reflected in the IS radial distribution function, g(r). Ayant et al. (139) proposed, independently, a very similar model incorporating the effects of molecular interactions. The same group has also dealt with the effects of spin eccentricity or translation-rotation coupling (140). 

The group in Grenoble has used the radial distribution function approach in a series of papers on intermolecular relaxation. We wish to mention in particular some of their papers from the 1990s, where the radial distribution functions were obtained through different approximate methods and a relatively simple description of the electron spin relaxation was applied (150-154). This work has also been reviewed (155,156). In a recent communication from the same group, the improved description of the electron spin relaxation in Gd(III) complexes (120,121) was included in the model and applied for... 

Fig. 10 Relaxation time distribution function/(r) describing the dielectric dispersion in relaxor PMN. The short timescale maximnm describes the glassy-type dynamics, whereas the long timescale part refers to the polar clnster dynamics. The same featnres are obtained in PMN, PLZT, and SEN relaxors...

---