The reactivity-selectivity principle: The derivation of bounds and a computational study

The decline of the reaction probability due to selectivity of the reaction with respect to the initial, reagents, states or with respect to the final, products, states is demonstrated analytically and by computational results for the H + H₂, F + H₂, and H + Cl₂ collinear reactive collisions. Upper and lower bounds on the reaction probability in terms of the entropy deficiency of the observed or computed products state distribution (or of the relative rates for state selected reagents) are derived and applied to the results of the collinear computations. For very selective processes, the maximal suprisal provides a tight bound for the (logarithm of the) reaction probability.