Unimolecular Processes and Vibrational Energy Randomization

Abstract

Intramolecular vibrational energy transfer is the subject of much current experimental and theoretical research. Some aspects of this problem are reviewed in this talk, together with a few new additions. Inasmuch as extensive references have been given in a recent review,¹ they are omitted in this extended abstract in the interests of brevity. Topics discussed include (1) experimental work, (2) some theoretical concepts on “regular” and “chaotic” motion in the classical and quantum mechanics of anharmonic systems, and (3) the question of whether experiments can distinguish regular from chaotic behavior. By way of introduction we begin first with a review of the unimolecular rate constant, of reactions occurring in the gas phase.