Semiclassical approach to the hydrogen-exchange reaction Reactive and transition-state dynamics

Abstract

Scattering matrix elements and symmetric transition-state resonances for the collinear H ₂ + H → H + H ₂ reaction are obtained using a time-dependent approach. The correlation function between reactant channel wavepackets and product channel wavepackets is used to determine the S-matrix elements. In a similar fashion, autocorrelation functions are used to extract the positions and widths of transition-state resonances. The time propagation of the wavepackets is performed by the improved semiclassical frozen Gaussian method of Herman and Kluk, which is an initial value, uniformly converged method. The agreement between the quantum and semiclassical results is far better than that obtained previously for this system by other semiclassical methods.