过渡金属活化甲烷的自旋禁阻反应的密度泛函理论研究-物理化学专业论文.docxVIP

硕士研究生：王强 硕士研究生：王强 专业：物理化学 II 导师：王永成教授 研究方向：化学动力学 Abstract Methane activation by transition metal has been a topic of growing interest during the past decade, due to economic interest in the methane conversion and chemistry. Interesting insights into the details and mechanisms of the activation process can be gained by studies of gas-phase reactions of metal ions and clusters. The activation of C-H bonds is a key step in numerous syntheic reactions and catalytic processes. Methane, as one of the most important chemicals, has been widely used in chemical synthesis, hydrogen production, and energy production. As such, methane activation has been studied extensively by both experimentalists and theorists. However, the activation of C-H bond in methane is a unique challenge among the hydrocarbons due to its large bond energy (the C-H bond energy is about 440 kJ/mol). Early investigations have shown that neutral metal atoms are often reacive under electronic excitation with small alkanes. Recent studies reveal that many transition metals including lanthanides and actinides are good C-H insertion agents in reactions with small alkanes and often form high-oxidation-state complexes with a carton-metal multiple bond following H migration. Methane activation mediated by W or Ta/ Ta- have generated new class of small insertion products and high-oxidation-state complexes with multiple carbon-metal bonds and was found to be a spin-forbidden process. According to the principle of two-state reactivity reaction, the activation of C-H bonds of methane by bare transition metal atom or cation had been examined using density functional theory to explore the reaction mechanisms. The whole paper consists of four chapters. Chapter 1 mainly reviews the progress and application of quantum chemistry as well as the development and the present situation of two-state reactivity. The second chapter summarizes the theoretical background of this thesis, mianly contained the potential energy