Dynamics of the Collinear H+H2 Reaction. I. Probability Density and Flux

Abstract

The time evolution of the collinear H+H2 reaction as given by classical mechanics and by time-dependent quantum mechanics has been studied. The calculations employed the Porter–Karplus potential surface. The relevant equations of motion were solved to high accuracy by direct numerical integration. The evolution of the quantal probability density in the interaction region of the potential surface is shown in a series of perspective plots. Classical mechanics gives an amazingly good description of the probability density and flux patterns during most of the reaction; however, the classical and quantal descriptions begin to diverge near the end of the reaction. Essentially, the classical reaction terminates before the quantal reaction. The dynamic behavior of the reaction is hydrodynamically turbulent, as shown by transient whirlpool formation on the inside of the reaction path. All results reported in this paper are for one average system energy, namely, 0.65 eV (initial average translational energy = 0.38 eV).