Role of direct and resonant (compound state) processes and of their interferences in the quantum dynamics of the collinear H + H2 exchange reaction

Abstract

The question of the relative importance of compound state (i.e., activated complex) and direct reaction mechanisms has been of central importance for the dynamical foundations of chemical kinetics [1,2]. The studies here reported indicate that in the quantum dynamics of the historically important H + H2 exchange reaction not only do both such mechanisms contribute but also that their interference plays a central role in determining the pronounced quantum oscillations of the reaction probability as a function of energy [3]. This accounts not only for the absence of such oscillations in quasiclassical calculations [4], but also for the inability of the present semiclassical formalism [5] to produce them [6].