Generalized relaxation equation

The generalized relaxation equation in terms of its components and in the frequency plane can be written as... 

Brace et al. [92] investigated polymer/water interactions using SAW devices coated with either polyimide or cellulose acetate butyrate (CAB). In this study thermodynamic parameters were evaluated from the absorption isotherms, and transient responses to step changes in concentration were monitored. The transient responses observed were not consistent with Fickian diffusion, but could be described using a generalized relaxation equation containing two additive terms. Results under various conditions indicated that relaxation in the polymer system is much slower than diffusion of water. 

In previous chapters phenomenological relaxation equations were used together with the Onsager regression hypothesis to compute time correlation functions. In this section we present a microscopic derivation of generalized relaxation equations (Zwan-zig, 1961 Berne, Mori, 1965 and 1971). These equations can be used to compute time-correlation functions under circumstances where the usual phenomenological equations do not apply. 

Eigen de Maeyer (1963 p. 903) have derived general relaxation equations for the exchange of ligands between two sites via two possible pathways ... 

The fimdamental kinetic master equations for collisional energy redistribution follow the rules of the kinetic equations for all elementary reactions. Indeed an energy transfer process by inelastic collision, equation (A3.13.5). can be considered as a somewhat special reaction . The kinetic differential equations for these processes have been discussed in the general context of chapter A3.4 on gas kmetics. We discuss here some special aspects related to collisional energy transfer in reactive systems. The general master equation for relaxation and reaction is of the type [H, 12 and 13, 15, 25, 40, 4T ] ... 

Keilson-Storer kernel 17-19 Fourier transform 18 Gaussian distribution 18 impact theory 102. /-diffusion model 199 non-adiabatic relaxation 19-23 parameter T 22, 48 Q-branch band shape 116-22 Keilson-Storer model definition of kernel 201 general kinetic equation 118 one-dimensional 15 weak collision limit 108 kinetic equations 128 appendix 273-4 Markovian simplification 96 Kubo, spectral narrowing 152... 

This is a second-order ODE with independent variable z and dependent variable k C t,z), which is a function of z and of the transform parameter k. The term C(t, 0) is the initial condition and is zero for an initially relaxed system. There are two spatial boundary conditions. These are the Danckwerts conditions of Section 9.3.1. The form appropriate to the inlet of an unsteady system is a generalization of Equation (9.16) to include time dependency ... 

In order to proceed now to a statistical mechanical description of the corresponding relaxation process, it is convenient to solve the equation of motion for the creation and destruction operators and cast them in a form ressembling a Generalized Langevin equation. We will only sketch the procedure. 

In the four preceding sections, we have developed various approximations for the relaxation term in the limiting law for the conductance of electrolytes, starting from the generalized transport equation (111). 

A general rate equation has been derived for reactions with a single relaxation time. Consider ... 

In the more general case where there may be surface interactions, i.e., a chemical exchange with surface sites where more efficient relaxation may occur, a term is added to the relaxation equation that is proportional to Ijd. The relaxation may generally be written as the sum of contributions ... 

If the paramagnetic center is part of a solid matrix, the nature of the fluctuations in the electron nuclear dipolar coupling change, and the relaxation dispersion profile depends on the nature of the paramagnetic center and the trajectory of the nuclear spin in the vicinity of the paramagnetic center that is permitted by the spatial constraints of the matrix. The paramagnetic contribution to the relaxation equation rate constant may be generally written as... 

Various theoretical formalisms have been used to describe chemical exchange lineshapes. The earliest descriptions involved an extension of the Bloch equations to include the effects of exchange [1, 2, 12]. The Bloch equations formalism can be modified to include multi-site cases, and the effects of first-order scalar coupling [3, 13, 24]. As chemical exchange is merely a special case of general relaxation theories, it may be compre-... 

We reemphasize that the foregoing relaxation equations containing the general shift-variant response-function element denoted by [s] m are equally valid for the special case of convolution, whether discrete or continuous. Cast in the continuous notation for convolution, the relaxation methods are epitomized by the repeated application of... 

Remarkably, when our general ME is applied to either AN or PN in Section 4.4, the resulting dynamically controlled relaxation or decoherence rates obey analogous formulae provided the corresponding density matrix (generalized Bloch) equations are written in the appropriate basis. This underscores the universality of our treatment. It allows us to present a PN treatment that does not describe noise phenomenologically, but rather dynamically, starting from the ubiquitous spin-boson Hamiltonian. 

Generalized local Darcy s model of Teorell s oscillations (PDEs) [12]. In this section we formulate and study a local analogue of Teorell s model discussed previously. The main difference between the model to be discussed and the original one is the replacement of the ad hoc resistance relaxation equation (6.1.5) or (6.2.5) by a set of one-dimensional Nernst-Planck equations for locally electro-neutral convective electro-diffusion of ions across the filter (membrane). This filter is viewed as a homogenized aqueous porous medium, lacking any fixed charge and characterized... 

In 1962 Fuoss and Onsager began a revision of their treatment of the conductance of symmetrical electrolytes. In their first paper they considered the potential of total force in the second, the relaxation field in the third, electrophoresis and in the fourth, the hydrodynamic and osmotic terms in the relaxation field (1,2,3,4). In 1965 Fuoss, Onsager, and Skinner (5) combined the results of the four papers and formulated a general conductance equation ... 

The relaxation equations for the time correlation functions are derived formally by using the projection operator technique [12]. This relaxation equation has the same structure as a generalized Langevin equation. The mode coupling theory provides microscopic, albeit approximate, expressions for the wavevector- and frequency-dependent memory functions. One important aspect of the mode coupling theory is the intimate relation between the static microscopic structure of the liquid and the transport properties. In fact, even now, realistic calculations using MCT is often not possible because of the nonavailability of the static pair correlation functions for complex inter-molecular potential. 

Finally, note that the method used by Kadanoff and Swift is a very general scheme. For example, the expression of ris[1H is similar to the expression of viscosity derived later by Geszti [39]. In addition, the projection operator technique used in their study is the same used to derive the relaxation equation [20], and the expression of Ly and Uy are equivalent to the elements of the frequency and memory kernel matrices, respectively. 

In order to find the Green s function g, we consider the diffusive case when the Usadel equation is applicable. This equation can be used provided the condition Jr momentum relaxation time). Of course, this condition can hardly be satisfied for strong ferromagnets like Fe and in this case one should use a more general Eilenberger equation for a quantitative... 

This adjustment process results in a change in the concentrations of some or all of the species. The rate of the adjustment to new equilibrium conditions or the rate of chemical relaxation is determined by the rate of the reactions that make up the equilibrium. By measuring the relaxation rate, one can obtain information that can be used to determine ki and k 1. Assume that the general rate equation... 

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