Quantization of chemical reaction: The dynamic correlation diagram method free from noncrossing rule

Abstract

Both Fukui's frontier orbital (FO) theory and Woodward-Hoffmann's orbital symmetry conservation (W-H) theory are based on the molecular orbital theory. However, there are some obvious inconsistencies between the two theories in explaining the electron movement. The process of chemical reactions has been explained by the potential surface analysis based on the time-independent Schrödinger equation. However, this approach is not always appropriate for describing unsteady states, because the variable of reaction coordinate should be time t by its very nature. When considering the time-scale of chemical reactions for molecules, there is inherent uncertainty in the energy levels for the midway state of chemical reactions owing to the Heisenberg uncertainty principle. The states which can be accurately described by quantum mechanics exist discontinuously in chemical reactions. Such quantization of chemical reactions solves all noncrossing problems. We also show that such an essential fact leads to new concepts and theories in chemical reactions such as stable molecule, elementary reaction and minimum deformation of orbital phases. Finally, taking the regularity in organic reactions as an example, we demonstrate that FO theory and WH theory can be unified consistently by the universally applicable "dynamic correlation diagram method." © 2012 World Scientific Publishing Company.