Quantum Mechanics of the H+H2 Reaction: Investigation of Vibrational Adiabatic Models

Abstract

The effects of reaction‐path curvature and angular‐momentum state on reactive H+H₂ collisions are investigated for the rotating linear model: three atoms constrained to a line with the line free to rotate in three‐dimensional space. Three vibrational adiabatic approximations to the quantum‐mechanical scattering problem are investigated after introducing Marcus' natural‐collision coordinates. Calculations based upon the Porter and Karplus H₃ surface are presented for the following reaction properties: local vibrational and translational energy, reaction probabilities, and reaction cross sections. Tunneling, the internal centrifugal effect, and the energy dependence of reaction coordinates are also considered.