Recent quantum dynamical calculations have shown that HO2 dissociates via isolated resonances, which have a distribution of rate constants that is statistical state-specific and well-described by the Porter-Thomas PE(k) distribution. In the work presented here, this PE(k) distribution is incorporated into RRKM theory to see how statistical fluctuations in state-specific rate constants affect the collision-averaged chemical activation rate constant k(ω, E) and the Lindemann-Hinshelwood thermal rate constant kuni(ω, T) for HO2 dissociation. Both active and adiabatic treatments are considered for the K quantum number. The calculations suggest the effect of statistical state specificity should be detectable in measurements of k(ω, E) and kuni(ω, T).
|Number of pages||5|
|Journal||Journal of Physical Chemistry A|
|State||Published - Feb 19 1998|