Relaxation Discrete

A single calculation of the discrete path integral with a fixed length of time t can be employed to compute the state conditional probability at many other times. It is possible to use segments of the path of time length At, 2At,..., NAt sampled in trajectories of total length of NAt and to compute the corresponding state conditional probabilities. The result of the calculations will make it possible to explore the exponential relaxation of P Ao B,t) for times between 0 and t. 

Flynn and Dickens [142] have translated the relaxation methods of fluid kinetics into terms applicable to solid phase thermogravimetry. The rate-determining variables such as temperature, pressure, gas flow rate, gas composition, radiant energy, electrical and magnetic fields are incremented in discrete steps or oscillated between extreme values and the effect on reaction rate determined. 

The velocity gradient leads to an altered distribution of configuration. This distortion is in opposition to the thermal motions of the segments, which cause the configuration of the coil to drift towards the most probable distribution, i.e. the equilibrium s configurational distribution. Rouse derivations confirm that the motions of the macromolecule can be divided into (N-l) different modes, each associated with a characteristic relaxation time, iR p. In this case, a generalised Maxwell model is obtained with a discrete relaxation time distribution. 

Third, writing the discretized equations in matrix form results in sparse matrices, often of a tri-diagonal form, which traditionally are solved by successive under- or over-relaxation methods using the tri-diagonal matrix algorithm... 

The discretized equations of the finite volume method are solved through an iterative process. This can sometimes have difficulty converging, especially when the nonlinear terms play a strong role or when turbulence-related quantities such as k and s are changing rapidly, such as near a solid surface. To assist in convergence a relaxation factor can be introduced ... 

The Fukui functions generalize the concept of frontier orbitals by including the relaxation of the orbital upon the net addition or removal of one electron. Because the number of electrons of an isolated system can only change by discrete integer number, the derivative in Equation 24.37 is not properly defined. Only the finite difference approximation of Equation 24.37 allows to define these Fukui functions (noted here by capital letters) F1 (r)... 

The product of m and G, could be replaced by a new elasticity, which for convenience we could write as Gj. Equations (4.41) and (4.42) describe the relaxation of the stress in terms of a distribution of discrete processes. Some processes may be broadly separated in time to give two clearly separated relaxation processes. Other systems may show a distribution of elastic processes very closely separated in time. 

One may consider the relaxation process to proceed in a similar manner to other reactions in electronic excited states (proton transfer, formation of exciplexes), and it may be described as a reaction between two discrete species initial and relaxed.1-7 90 1 In this case two processes proceeding simultaneously should be considered fluorescence emission with the rate constant kF= l/xF, and transition into the relaxed state with the rate constant kR=l/xR (Figure 2.5). The spectrum of the unrelaxed form can be recorded from solid solutions using steady-state methods, but it may be also observed in the presence of the relaxed form if time-resolved spectra are recorded at very short times. The spectrum of the relaxed form can be recorded using steady-state methods in liquid media (where the relaxation is complete) or using time-resolved methods at very long observation times, even as the relaxation proceeds. 

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