Study of the Transition State Region in the Cl + HCl Reaction by Photoelectron Spectroscopy of ClHCl(-)

摘要

A central goal of reaction dynamics has been to gain a microscopic understanding of chemical bond formation and cleavage during a reactive collision. This requires a knowledge of the potential energy hypersurface for a chemical reaction especially near the transition state, as this is the region of the surface that determines the outcome of a collision. Our experiments represent a significant departure from the state-to-state chemistry approach to this problem which has been developed over the last ten years. We probe the transition state region for a neutral reaction not by a collision, but rather by photodetachment of a stable anion geometrically similiar to the neutral transition state. Specifically, we have studied the Cl + HCl and Cl + DCl hydrogen exchange reactions by photoelectron spectroscopy of ClHCl(-) and ClDCl(-).