The effect of reagent vibrational excitation on the oscillatory behavior and other dynamical properties of the light-atom-transfer reactions Cl + HCl → ClH + Cl and O + HCl → OH + Cl

Abstract

A three-dimensional quasiclassical trajectory study was carried out to investigate the effect of reagent vibrational excitation on several dynamical properties of the light-atom-transfer reactions Cl + HCl → ClH + Cl and O + Hcl → OH + Cl for various types of potential energy surfaces. These properties are the oscillatory behavior of partial cross sections as a function of collision energy, the influence of reagent rotation on reaction cross sections, and the rotational excitation of the products. Earlier studies for ground vibrational state reagents (ν = 0) showed that these properties correlate well with features of potential energy surfaces. It was found that vibrational excitation of the reagents causes a significant amplification of the oscillatory behavior for all types of surfaces and leaves the dependence of reaction cross sections on reagent rotation unchanged qualitatively. The differences in the rotational energy of the products for different types of surfaces, while still significant for ν= 1, tend to decrease with reagent vibrational excitation. The present results indicate an obvious advantage in using vibrationally excited reagents in experimental investigations of oscillations in reaction cross sections. They also indicate that studies with rovibrational state selected reagents can provide significant information concerning the nature of potential energy surfaces for heavy+light-heavy→heavy-light+heavy bimolecular reactions.