Natural Bifurcation Coordinates for Three-Dimensional Chemical Reactions

Abstract

Three‐dimensional atom‐diatom collisions which can lead to two possible rearrangement products are considered under the restraint of near‐linear intermediates. A coordinate system (natural bifurcation coordinates) is introduced to provide for smooth internal rotation of the system in the region of reaction path bifurcation; thus systems are allowed to ``wobble'' from one reaction path to the other. For both two‐ and three‐dimensional reactions, the Hamiltonian operator is derived from the classical kinetic energy.