A Chemists Guide to Density Functional Theory-13 Chemical Reactivity-Exploring Potential Energy Surfaces.Image.Marked资料.pdf

A Chemist’s Guide to Density Functional Theory. Second Edition Wolfram Koch, Max C. Holthausen Copyright © 2001 Wiley-VCH Verlag GmbH ISBNs: 3-527-30372-3 (Softcover); 3-527-60004-3 (Electronic) 13 Chemical Reactivity: Exploring Potential Energy Surfaces The rates of chemical reactions are in many cases limited because of the presence of energy barriers between reactants and products, and the barrier heights typically determine the branching ratio of products. A rigorous understanding of all elementary steps along the reaction coordinates leading from reactants to products is a prerequisite for the develop- ment of guidelines for rationalizing or predicting the corresponding chemical transforma- tions. However, the complete characterization of the actual reaction mechanisms, i. e., ex- plicit information on the structural and energetic details of all intermediates and transition structures relevant in the course of a particular reaction, by experimental means alone has 58 been possible in only a very limited number of cases. Quantum chemical calculations offer in principle a complementary source of information. Among the most prominent ap- plications of modern electronic structure theory is therefore the localization and characteri- zation of stationary points on those parts of a potential energy surface, which are associated with a chemical reaction. In particular the ability to directly model the transition structures connected to the activation barriers is a most appealing feature. However, even for a quali- tatively correct picture of a reaction path electron correlation effects need to be taken into account in the framework of conventional ab initio molecular-orbital