title: How much can an intermediate state influence competing reactive pathways?
abstract: A molecule undergoing reaction may form a short-lived intermediate. Under certain conditions, the rate at which the reaction proceeds toward the product state via the intermediate may exceed that of a simple, direct path. The competition of two alternative reactive pathways is analyzed here in terms of a stochastic model. The approach allows one to diagnose this competition as a function of the energy of the intermediate relative to the barrier heights of the potential surface and values of the reactive vibrational modes. The result has applications to a variety of problems in chemical physics, ranging from the "lock-and-key" mechanism for the enzymatic activity to control of temporal evolution of complex systems by optimal laser fields.
authors.affiliation: Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, USA.
authors.forename: Florin
authors.initials: F
authors.lastname: Despa
authors.forename: R Stephen
authors.initials: RS
authors.lastname: Berry