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Measurement and Analysis of Atomic Hydrogen and Diatomic Molecular AlO, C2, CN, and TiO Spectra Following Laser-induced Optical Breakdown
Published on: February 14, 2014
Quantum dynamics analysis of transition-state spectrum for the SH + H2S → H2S + SH reaction
1Department of Chemistry, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570, Japan. tako@mail.saitama-u.ac.jp.
Abstract:
We present the results of quantum wave packet calculations analyzing the experimental transition-state spectrum for the SH + H2S hydrogen transfer reaction based on photodetachment of the H3S2- anion. We used a reduced-dimensionality model in which four normal-mode coordinates were considered for the dynamics of the neutral transition state. The four-dimensional potential energy surfaces for the anionic and neutral states were constructed using four different levels of theory, namely, MP2, B3LYP, CAM-B3LYP, and LC-BLYP, with the aug-cc-pVDZ basis set. The spectrum calculated using the scaled MP2 potential energy surface was in reasonable agreement with the experimental spectrum. The present theoretical study confirms that the vibrational progression observed experimentally is associated with the antisymmetric motion of the transferred hydrogen atom. We also found that the S-S stretching motion plays an important role in the transition-state dynamics.
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