Exit routes from the transition state: Angular momentum constraints on the formation of products

McCaffery, Anthony J, Osborne, Mark A and Marsh, Richard J (2005) Exit routes from the transition state: Angular momentum constraints on the formation of products. Journal of Physical Chemistry A, 109 (23). pp. 5005-5015. ISSN 1089-5639

Full text not available from this repository.


We have analyzed experimental data from a number of exothermic processes in which molecules in well-defined initial states are deactivated by inelastic, dissociative, or reactive collisions. Further, we analyze deactivation processes that do not occur in molecules despite their containing high levels of excitation. Significant common elements are found among these forms of deactivation. The initial step consists of transition to a product state involving minimum rotation state change (Delta j) consistent with energy conservation. Frequently, this process is near-energy-resonant. More critically, it may frequently require substantial angular momentum (AM) change. Analysis of experimental data indicates that constraints act upon on the formation of products in processes that involve release of excess energy. These constraints are associated with the magnitude of AM that must be generated for the initial transition to occur and this AM "load" increases with the amount of energy to be released. In general, the probability of generating rotational AM falls rapidly as Delta j increases, and this effectively limits the size of energy gap that may be bridged by a given reactant pair and at some point the constraint is sufficient to constitute a barrier that prevents the process from taking place. The choice of reactant species strongly affects the probability of each process that increases (i) when molecules efficiently interconvert momentum and (ii) when many product states are available in the critical near-resonant region. These factors increase the proportion of initial trajectories that possess the energy and momentum necessary to open a "product" channel. Evidence is presented showing that AM load-reduction strategies lead to marked enhancement of rates of collision-induced processes, suggesting that reduction of constraints in the exit channels from the transition state may constitute a previously unrecognized form of catalysis.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Depositing User: Anthony McCaffery
Date Deposited: 06 Feb 2012 19:19
Last Modified: 21 Mar 2012 15:01
URI: http://srodev.sussex.ac.uk/id/eprint/20097
📧 Request an update