title: Photodetachment-photoelectron spectroscopy of HS- x H2S and DS- x D2S: the transition states of the SH + H2S and SD + D2S reactions.
abstract: 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.
authors.affiliation: Technische Universität München, Physical Chemistry, 85748 Garching, Germany.
authors.forename: Michaela
authors.initials: M
authors.lastname: Entfellner
authors.forename: Daniel
authors.initials: D
authors.lastname: Opalka
authors.forename: Ulrich
authors.initials: U
authors.lastname: Boesl
mesh_terms: D003903:Deuterium / Q000737:chemistry*; D041961:Deuterium Exchange Measurement; D006862:Hydrogen Sulfide / Q000737:chemistry*; D013058:Mass Spectrometry; D056951:Photoelectron Spectroscopy
chemical_list: D003903:Deuterium; D006862:Hydrogen Sulfide