Reaction Dynamics Study of the Molecular Hydrogen Loss Channel in the Elementary Reactions of Ground-State Silicon Atoms (Si(3P)) With 1- and 2-Methyl-1,3-Butadiene (C5H8)
| Autor: | Ralf I. Kaiser, Zhenghai Yang, Shane J. Goettl, Chao He |
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| Rok vydání: | 2021 |
| Předmět: |
010304 chemical physics
Silicon Chemistry chemistry.chemical_element 010402 general chemistry 01 natural sciences Transition state 0104 chemical sciences Crossed molecular beam Intersystem crossing Chemical physics Reaction dynamics 0103 physical sciences Elementary reaction Singlet state Physical and Theoretical Chemistry Ground state |
| Zdroj: | The Journal of Physical Chemistry A. 125:5040-5047 |
| ISSN: | 1520-5215 1089-5639 |
| Popis: | The bimolecular gas-phase reactions involving ground-state atomic silicon (Si; 3P) and 1- and 2-methyl-1,3-butadiene were studied via crossed molecular beam experiments. Our data revealed indirect scattering dynamics through long-lived SiC5H8 collision complex(es) along with molecular hydrogen loss pathways, leading to facile formation of SiC5H6 isomer(s). We propose that the reactions of silicon with 1- and 2-methyl-1,3-butadiene possess reaction dynamics in an analogy to the silicon-1,3-butadiene system. This leads to cyclic methyl-substituted 2-methylene-1-silacyclobutene isomers via nonadiabatic reaction dynamics through intersystem crossing (ISC) from the triplet to the singlet surface in overall exoergic reactions through tight exit transition states and molecular hydrogen loss. Our study also suggests that the methyl group-although a spectator from the chemical viewpoint-can influence the disposal of the angular momentum into the rotational excitation of the final product. |
| Databáze: | OpenAIRE |
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