Collision Model of `Fall-Off´ in Recombination Reactions

Abstract

Assuming random, multiple collisions the 'fall-off' problem in chemical recombination reactions is reconsidered. Following this approximative model the 'fall-off' from third order reactions at low pressure to second order reactions at high pressure appears in a simple way as a consequence of the collision time considered as the lifetime of the unstable van der Waals complex formed initially in the recombination mechanism.Comparisons are presented for results from the 'fall-off' following the Lindemann type mechanism, and of the method of Troe, Gilbert et al. based on the RRKM theory, together with some experimental results for recombination reactions at low and intermediate pressures. *

Rotational effects in broadening factors of fall-off curves of unimolecular dissociation reactions

“…After having analyzed the magnitude of broadening factors through the center broadening factors in Section 3, in the following we look at asymmetries which are not accounted for by eqn. ( 18) and (19). Instead of following the approach of ref.…”