Asymmetric internal rotation: Application to the 2-C4H9CH3+C3H6 reaction

Abstract

The unimolecular dissociation is examined using a combination of master equation, transition-state theory and inverse Laplace transform techniques. All these techniques require a knowledge of the density of states of the species involved. The contribution of hindered internal rotation to the density of states is treated using classical mechanics recognising the interaction between internal and external rotation. Rate data from direct measurement of k ₁ are analysed using this approach and rate parameters extracted. NASA polynomial fits of thermodynamic quantities and analytical representation of fall-off data using the method of Troe are also presented.