Theoretical Studies of Hot-Atom Reactions. I. General Formulation

Abstract

A general treatment of hot‐atom reactions is developed to facilitate correlation with molecular‐beam and theoretical studies of collision dynamics. Effects of the velocity distributions of the gases in the reaction mixture, inelastic processes, collisional isotope effects, and the temperature dependence of the integral‐reaction probability are included in the formalism. The basic integral equation may be solved by iteration for the integral reaction probability (relative yield) as a function of hot‐atom energy. Since there is no restriction on the range of energies over which the equation is valid, the theory is equally applicable to photochemically induced and nuclear‐recoil‐induced hot‐atom reactions. The relationship of the treatment to earlier formulations is discussed.