Dissociation and Isomerization of Vibrationally Excited Species. II. Unimolecular Reaction Rate Theory and Its Application

Abstract

Data on quasi‐unimolecular reactions have usually been compared with theoretical equations based on classical treatments, because the expressions are simpler than those obtained on the basis of a quantum model. The quantum reformulation of the RRK theory in Part I is used to compute the pressure dependence of the rate constants and the limiting low‐pressure rates for a variety of unimolecular reactions without employing adjustable parameters. An asymptotic expansion of the integral for the limiting low‐pressure second‐order rate constant provides a very simple expression for this quantity. The errors inherent in corresponding classical calculations are estimated by comparing these results with those obtained from the theory in its classical limit. The error is temperature dependent and at low pressures increases from a factor of about three (under typical experimental conditions) for small reactants such as O₃ and N₂O to 10⁵ or more for large molecules such as cyclopropane, C₂H₆, and N₂O₅. In most cases the rates calculated from the quantum form are in reasonable agreement with those obtained experimentally when all of the reactant oscillators are assumed effective in intramolecular energy transfer.