Morse bifurcations of transition states in bimolecular reactions

Abstract

The transition states and dividing surfaces used to find rate constants for bimolecular reactions are shown to undergo qualitative changes, known as Morse bifurcations, and to exist for a large range of energies, not just immediately above the critical energy for first connection between reactants and products. Specifically, we consider capture between two molecules and the associated transition states for the case of non-zero angular momentum and general attitudes. The capture between an atom and a diatom, and then a general molecule are presented, providing concrete examples of Morse bifurcations of transition states and dividing surfaces. The reduction of the $n$-body systems representing the reactions is discussed and reviewed with comments on the difficulties associated with choosing appropriate charts and the global geometry of the reduced spaces.

Final/published version - shortened wrt V1

References in corpus (3)

• Multiple Transition States and Roaming in Ion-Molecule Reactions: a Phase Space Perspective
• Bifurcations of transition states: Morse bifurcations
• Phase space structures governing reaction dynamics in rotating molecules

Cited by in corpus (4)

• Phase space barriers and dividing surfaces in the absence of critical points of the potential energy: Application to roaming in ozone
• Tilting and Squeezing: Phase space geometry of Hamiltonian saddle-node bifurcation and its influence on chemical reaction dynamics
• The phase space geometry underlying roaming reaction dynamics
• Influence of mass and potential energy surface geometry on roaming in Chesnavich's CH${}_4^{+}$ model