From quantum chemistry to dissociation kinetics: what we need to know

Abstract

The relationship between rate constants for dissociation and the reverse association reactions and their potential energy surfaces is illustrated. The reaction systems e− + SF6 ↔ SF6− →SF5− + F, H + CH3 ↔CH4, 2 CF2 ↔ C2F4, H + O2 →HO2, HO + O ↔HO2 ↔ H + O2, and C + HO →CHO are chosen as representative examples. The necessity to know precise thermochemical data is emphasised. The interplay between attractive and anisotropic components of the potentials influences the rate constants. Spin–orbit and electronic–rotational coupling in reactions between electronic open-shell radicals so far generally has been neglected, but is shown to have a marked influence on low temperature rate constants.