In this paper, we discuss the experimental technique for real-time measurement of the lifetimes of the collision complex of bimolecular reactions. An application to the atom–molecule Br+I_2 reaction at two collision energies is made. Building on our earlier Communication [J. Chem. Phys. 95, 7763 (1991)], we report on the observed transients and lifetimes for the collision complex, the nature of the transition state, and the dynamics near threshold. Classical trajectory calculations provide a framework for deriving the global nature of the reactive potential energy surface, and for discussing the real-time, scattering, and asymptotic (product-state distribution) aspects of the dynamics. These experimental and theoretical results are compared with the extensive array of kinetic, crossed beam, and theoretical studies found in the literature for halogen radical–halogen molecule exchange reactions
