Generalized perturbation theory homogeneous systems

The development and application of generalized perturbation theory (GPT) has made considerable progress since its introduction by Usachev (i(S). Usachev developed GPT for a ratio of linear flux functionals in critical systems. Gandini 39) extended GPT to the ratio of linear adjoint functionals and of bilinear functionals in critical systems. Recently, Stacey (40) further extended GPT to ratios of linear flux functionals, linear adjoint functionals, and bilinear functional in source-driven systems. A comprehensive review of GPT for the three types of ratios in systems described by the homogeneous and the inhomogeneous Boltzmann equations is given in the book by Stacey (41). In the present review we formulate GPT for composite functionals. These functionals include the three types of ratios mentioned above as special cases. The result is a unified GPT formulation for each type of system. 

The generalized perturbation theory expressions presented in this section for systems described by the homogeneous Boltzmann equation (excluding Section V,B,2) are in the form proposed by Stacey (40, 41). Had we assumed that the overall alteration in the reactor retains criticality, we would have achieved the Usachev-Gandini version of GPT. Stacey s version is often associated (41, 46, 48, 62) with the variational perturbation theory as distinguished from the GPT of Usachev-Gandini. Does the variational approach provide a different perturbation theory than the GPT derived (35,39) from physical considerations Is one of these versions of perturbation theory more general or more accurate than the other What does the term GPT stand for ... 

Quantum mechanical approaches for describing electron transfer processes were first applied by Levich [4] and Dogonadze, and later also in conjunction with Kuznetsov [5]. They assumed the overlap of the electronic orbitals of the two reactants to be so weak that perturbation theory, briefly introduced in the previous section, could be used to calculate the transfer rate for reactions in homogeneous solutions or at electrodes. The polar solvent was here described by using the continuum theory. The most important step is the calculation of the Hamiltonians of the system. In general terms the latter are given for an electron transfer between two ions in solution by... 

Generalized-function formulations of GPT for homogeneous systems are the source of sensitivity functions for different integral parameters Equation (189) for reactivity worths, and Eq. (162) for ratios of linear and bilinear functionals. The first-order perturbation theory expression for reactivity [Eq. (132)] can also be used for sensitivity studies. 

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