The kinetics of internal energy randomisation in thermal unimolecular reactions

Abstract

The aim of this paper is to present a minimal theory of thermal unimolecular reactions, including explicitly the kinetics of intramolecular randomisation processes. A quasi-diatomic model is formulated and, within the framework of the model, both first-and second-order randomisation processes among reactant and product states are examined.It is concluded that a vital mechanism for the intramolecular energy randomisation in thermal unimolecular reactions is a collisional one. On this assumption, a straightforward derivation of the Polanyi–Wigner specific rate function, as we have reinterpreted it, becomes possible.At the same time, anomalies in the fall-off curves for the thermal isomerisations of methyl isocyanide and ethyl isocyanide can be accounted for very simply: in the former case, values for both the first- and second-order randomisation rate constants can be derived, but in the latter case it is only possible to establish a lower limit for the second-order randomisation rate constant.