The transition state region for neutral hydrogen transfer reactions can be accessed by photodetachment of a stable negative ion with a geometry similar to that of the neutral transition state. In this work the SH + H(2)S and SD + D(2)S reactions are investigated by photodetachment-photoelectron spectroscopy of HS(-) x H(2)S and DS(-) x D(2)S. The spectra exhibit vibrational structure which is attributed to the antisymmetric stretching mode (H-atom motion) of the neutral transitions state for H-atom transfer. The spectra are compared to one-dimensional simulations performed using a wave packet propagation scheme. Electronic structure calculations of the anionic, neutral and transition-state geometries and calculations of the vertical detachment energy at different levels of theory are used to support the analysis of the spectra. A vertical detachment energy VDE of 3.06 eV has been determined.
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