Unimolecular dissociation energy-averaged rate

Comparison of the HO2 -> H + O2 unimolecular dissociation rates as obtained from the quantum mechanical resonances (kqm, open circles) and from variational transition state RRXM, theory (kuRKM, step function). E,i,f is the threshold energy for dissociation. Also shown is the quantum mechanical average of the as in a AF = 0.075 eV energy interval (kq, solid line) and the experimental prediction (dashed line). Adapted from ref. 122. 

The energy loss itself is the product of the time it takes the particle to return to the barrier and the energy loss per unit time. This time, on the average is just the inverse of the RRKM unimolecular, canonical dissociation rate ... 

The plots in Fig. 3 clearly show that the initial dissociation rates are strongly affected by the excitation process. Putting energy near the reaction site promotes unimolecular reaction, while the opposite is observed if the energy is put at a site that is removed from the reaction site. However, analyses of the lifetime distributions show that by 10 s the decomposition probabilities have become statistical. Since the average RRKM lifetime for H-CEC-Cl is greater than... 

---