Metastable Component Of The Electron Transfer Dynamics Study

In this thesis, two important chemical questions in the field of molecular reaction dynamics, namely the weak interaction and the electron transfer reaction have been relative. It includes five chapters. At first, several problems relate to the electron transfer reaction are introduced, then relative calculation methods are represented, after that the intermediate and the activation energy, the potential energy surface, the electronic coupling matrix element and the electron transfer rate of the system are discussed in detail, at last our own opinion have been put forward. All findings are the first reports and have been published or accepted. The main problems that involved in this thesis can be come down to the following five points:1. Intermediate : For the electron transfer reaction, the Encounter Complex, also termed as the Precursor Complex, is the first stage of the ET reaction. Because the geometrical configuration of the encounter/precursor complex influences directly both in the activation energy of reaction and in the ET coupling matrix element and further in the ET rate, thus it is very important to find various possible geometrical configurations for the encounter complex.2. Potential Energy Surface: On the basis of the analysis of the potential energy surface the character of the electron transfer reaction, the component of the potential energy surface and the key factors that affect the potential energy have been pointed out. Through the scanning, it was found that the DFT methods in predicting the energy curves especially with long contact distance in which the DFT methods give the abnormal behavior for the dissociation of thecomplexes due to the "inverse symmetry breaking" problem. The fitted polynomial indicates that the Moller-Plesset theory method can basically produce normal dissociation behavior when dealing with the electron transfer problem. 3. Activation Energy: On the basis of the potential energysurface character, the potential energy surface of the reactant and the production can be disassembled into the contribution of the acceptor, the donor and their coupling, and can be composed by their potential energy surface. In the circumstance of no approximation was draught in, giving the activation parameters of the reactant at the transition state and the scheme to determine the activation energy, educe the material expression of the self-exchange reaction. The dependence of the activation energy on the contact distance and the varies factors that effect the activation energy have been discussed in this thesis.4. Electron Coupling Matrix Element: it is clear thatthe ET rate depends strongly on the electronic coupling matrix element, and the ET rate (kef) is in direct proportion with the square of the electronic coupling matrix element (|Hif|2). The larger the electronic coupling matrix element is, the faster the ET rate is. The key factor that effect the ECME has been determined, and the dependence of the ECME on the contact distance has also been discussed, 5. Electron Transfer Rate: it is obvious that if theelectronic coupling matrix element Hjf and the final-state density (p) have been calculated, the electron transfer rate is very easy to be calculated. It is pointed out that the effect of the coupling modes or the orientations on the electron transferrate. The relation of the ET rate and the contact distance has also been determined. The Golden-rule has been applied in dealing with the electron transfer.The most valuable results in this thesis can be come down to the following five points:1. Through the research it was found that the DFT methods in predicting the energy curves especially with long contact distance in which the DFT methods give the abnormal behavior for the dissociation of the complexes due to the "inverse symmetry breaking" problem. But the Moller-Plesset method is reliable in further discussing abou...