Quantum mechanical theory of collisional recombination rates. Part 2.—Beyond the strong collision approximation

Abstract

A quantum mechanical theory of collisional recombination (within the Lindemann mechanism, A + B ↔ AB*, AB*+ M → AB + M) is presented which provides a proper quantum description of the A + B collision dynamics and treats the M + AB* inelastic scattering within the impact approximation (the quantum analogue of a classical master equation treatment). The most rigorous version of the theory is similar in structure to the impact theory of spectral line broadening and involves generalized (four-index) rate constants for describing M + AB* collisions. A simplified version is also presented which involves only the normal (two-index) inelastic rate constants for M + AB* scattering but which also retains a proper quantum description of the A + B dynamics.