TRANSITION-STATE SPECTROSCOPY AND THE UV ABSORPTION-SPECTRA OF H2O AND H2S - EMISSION-SPECTROSCOPY AS A PROBE OF DYNAMICS ALONG REACTIVE TRAJECTORIES WHICH SAMPLE A RESONANCE

Firstly the underlying connection between the negative ion photodetachment studies of the "transition state spectroscopy" of neutral bimolecular reactions and previous measurements of the structure in the absorption spectra of H2O and H2S are detailed. This structure, being assigned to recurrences in the motion along the symmetric stretch coordinate on the saddle point region of the first excited state, a motion orthogonal to the reaction coordinate on the excited H + SH or H + OH reactive potential energy surfaces. represents the spectroscopy of the transition state. We then describe how our recent measurement of the emission spectrum of dissociating H2S Selectively accesses a particular resonance and probes the evolution of the dynamics into the exit channel of the reactive trajectories. Such dynamics cannot be probed in photodetachment studies, which necessarily form the neutral collision complex at a wide range of energies, not just within a chosen resonance.