Chemical reaction theory for asymmetric atom–molecule collisions

Abstract

A theoretical framework for describing the quantum dynamics of an atom–diatom system (A+BC) in three physical dimensions is presented. This theory explicitly treats the case where A, B, and C are each distinct, and hence no simplifications arise from the symmetry of a homonuclear diatomic. A natural collision coordinate system, depending primarily on the masses A, B, and C and the asymptotic potential energy surface is engineered appropriate to the system yielding a tractable expression for the kinetic energy operator. Close coupled equations for both free and hindered rotor expansions of the wavefunction are derived and the matching procedure and boundary conditions required to obtain the full scattering matrix (S matrix) are given.