Reactant States Model: Predicted k(E,J) for NO2(2A1)----> O(3P) + NO(2II), Based on Spectroscopic Data

BEATRIZ M. TOSELLI; JOHN R. BARKER

AMER INST PHYSICS

Año: 1989 p. 2239 - 2239

High-order spectroscopic data for the reactant are used exclusively to determine both the sumof open reactive channels and the density of states, which are used in a statistical theory topredict dissociation rate constants. Practical methods are introduced for calculating sums ofreactive channels and densities of states, when couplings among all degrees of freedom areincluded. An empirical method is described for reconciling spectroscopic parameters withknown dissociation energies (also determined spectroscopically). The predicted k(E,J),s andthermal kw (n for N02 dissociation are in good agreement with experimental data, especiallywhen the effects of electronically excited states are included. The predicted low pressurethermal rate constants are generally in fair agreement with experiment, although a slightlydifferent temperature dependence is calculated; this discrepancy is probably due to the absenceof unknown higher orde