Issue 35, 2020

Quantum dynamics analysis of transition-state spectrum for the SH + H2S → H2S + SH reaction

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.

Graphical abstract: Quantum dynamics analysis of transition-state spectrum for the SH + H2S → H2S + SH reaction

Supplementary files

Article information

Article type
Paper
Submitted
08 Jun 2020
Accepted
11 Aug 2020
First published
11 Aug 2020

Phys. Chem. Chem. Phys., 2020,22, 19845-19854

Quantum dynamics analysis of transition-state spectrum for the SH + H2S → H2S + SH reaction

T. Takayanagi, Phys. Chem. Chem. Phys., 2020, 22, 19845 DOI: 10.1039/D0CP03072D

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