“Direct” and “Correct” Calculation of Canonical and Microcanonical Rate Constants for Chemical Reactions

摘要: Theoretical approaches for calculating rate constants of chemical reactionseither the microcanonical a given total energy k(E) or canonical temperature k(T)are described that are both “direct”, i.e., bypass necessity having to solve complete state-to-state quantum reactive scattering problem, yet also “correct”, in principle exact (given potential surface, assuming nonrelativistic mechanics, etc.) Applications variety reactions presented illustrate methodology various dynamical situations, e.g., transition-state-theory-like dynamics where system moves directly through interaction (transition-state) region and form long-lived collision complexes. It is shown how this rigorous theory can be combined with Lindemann mechanism describing effects collisions bath gas, so as able treat recombination other pressure. Finally, several ways ...