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
✍ Scribed by L.J. Butler
- Publisher
- Elsevier Science
- Year
- 1991
- Tongue
- English
- Weight
- 598 KB
- Volume
- 182
- Category
- Article
- ISSN
- 0009-2614
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✦ Synopsis
Firstly the underlymg 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 Ha0 and Ha.3 are detailed. This structure, being assigned to recurrences in the motion along the symmetrtc stretch coordinate on the saddle point region of the first excited state. a motion orthogonal to the reaction coordinate on the excited Hf SH or H tOH reactive potential energy surfaces, represents the spectroscopy of the transition state. We then descrrbe how our recent measurement of the emission spectrum ofdissociating HaS 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.