Van der Waals Molecules as a Vehicle for the Study of Unimolecular Reactions

摘要: The general aspects of the dynamics thermal unimolecular reactions were elucidated in 1920’ by introduction three key ideas. First, Lindemann hypothesis1 provided an explanation, using phenomenological formulation reaction kinetics, how collisional excitation molecules can be consistent with first order kinetics high pressure regime while being, course, second low regime. Although qualitatively satisfactory, application hypothesis its simplest form predicts that transition as a function from to occurs at much higher presure than is observed.2 Second, Hinshelwood theory3 introduced notion rate constant for energization process greater complex molecule simple because energy distributed over larger number degrees freedom. analysis removes above mentioned problem respect dependence rate. Third, Rice-Kassel-Ramsberger (RKR) theory4