Intramolecular rate process: Isomerization dynamics and the transition to chaos

Abstract
The Hamiltonian flow of a system of two degrees of freedom, capable of undergoing geometrical isomerization, is studied as a function of the coupling between the reactive and unreactive degrees of freedom. The reaction dynamics are analyzed from the perspective of the KAM theorem and the transition to chaos. Conditions are found for the validity of linear rate laws and RRKM theory in isolated molecules.