Quantum diffusion theory system

Part A. Quantum-Mechanical Theory of Diffusion Independent Electron Transfer in Biological Systems by Ephraim Buhks (University of Delaware)... 

The solution of (2.3.69) is a purely mathematical problem well known in the theory of diffusion-controlled processes of classical particles. However, a particular form of writing down (2.3.69) allows us to use a certain mathematical analogy of this equation with quantum mechanics. Say, many-dimensional diffusion equation (2.3.69) is an analog to the Schrodinger equation for a system of N spinless particles B, interacting with the central particle A placed... 

The structures of the surfaces, the surface adsorption and the alkali-doped crystal and the atom diffusion path (cf. Section 4) were investigated by different quantum-chemical methods. We used foremost ab initio methodologies. The main computational tool utilized was the program CRYSTAL [54]. This program makes it possible to treat molecules and in particular crystalline solids and surfaces at an ab initio level of theory for surfaces and solids the periodic boundary conditions are applied in 2 or 3 dimensions [55]. The familiar Gaussian basis sets can be used for systems ranging from crystals to isolated molecules, which enables systematic comparative studies of chemical properties in different forms of matter. In our studies, split-valence basis sets were used [56]. 

An important issue of the application of electronic structure theory to polyatomic systems is the selection of the appropriate basis set. As usual in quantum chemistry, a compromise between precision and computational cost has to be achieved. It is generally accepted that in order to obtain qualitatively correct theoretical results for valence excited states of polyatomic systems, a Gaussian basis set of at least double-zeta quality with polarization functions on all atoms (or at least on the heavy atoms) is necessary. For a correct description of Rydberg-type excited states, the basis set has to be augmented with additional diffuse Gaussian functions. Such basis sets were used in the calculations discussed below. 

Thus, the assumption of the decoherence theory that there are no isolated systems, and that we have always to consider the influence of environmental fluctuations, would kill anomalous diffusion. Furthermore, the numerical results of Ref. 31 show that the quantum-induced transition from anomalous to ordinary diffusion is a quantum effect more robust than the localization phenomenon itself. This indicates that in the presence of a weak environmental fluctuation is now insufficient to reestablish the correspondence principle. 

We have seen that decoherence theory, according to its advocates [128], makes the wave-function collapse assumption obsolete The environmental fluctuations are enough to destroy quantum mechanical coherence and generate statistical properties indistinguishable from those produced by genuine wave-function collapses. All this is unquestionable, and if a disagreement exists, it rests more on philosophy than on physical facts. Thus, there is apparently no need for a new theory. However, we have seen that all this implies the assumption that the environment produces white noise and that the system of interest, in the classical limit, produces ordinary diffusion. As we move from... 

In general, for each acid HA, the HA-(H20) -Wm model reaction system (MRS) comprises a HA (H20) core reaction system (CRS), described quantum chemically, embedded in a cluster of Wm classical, polarizable waters of fixed internal structure (effective fragment potentials, EFPs) [27]. The CRS is treated at the Hartree-Fock (HF) level of theory, with the SBK [28] effective core potential basis set complemented by appropriate polarization and diffused functions. The W-waters not only provide solvation at a low computational cost they also prevent the unwanted collapse of the CRS towards structures typical of small gas phase clusters by enforcing natural constraints representative of the H-bonded network of a surface environment. In particular, the structure of the Wm cluster equilibrates to the CRS structure along the whole reaction path, without any constraints on its shape other than those resulting from the fixed internal structure of the W-waters. 

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