Gas‐Phase Formation of the Disilavinylidene (H 2 SiSi) Transient
| Autor: | John F. Stanton, Bing-Jian Sun, Thanh Lam Nguyen, Kang‐Heng Chao, Tao Yang, Ralf I. Kaiser, Beni B. Dangi, Agnes H. H. Chang |
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| Rok vydání: | 2017 |
| Předmět: |
Silicon
Hydrogen 010405 organic chemistry chemistry.chemical_element General Medicine 02 engineering and technology General Chemistry 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences Silane Catalysis 0104 chemical sciences Crossed molecular beam symbols.namesake chemistry.chemical_compound Intersystem crossing chemistry Computational chemistry Chemical physics Reaction dynamics symbols Singlet state van der Waals force 0210 nano-technology |
| Zdroj: | Angewandte Chemie International Edition. 56:1264-1268 |
| ISSN: | 1521-3773 1433-7851 |
| Popis: | The hitherto elusive disilavinylidene (H2SiSi) molecule, which is in equilibrium with the mono-bridged (Si(H)SiH) and di-bridged (Si(H2)Si) isomers, was initially formed in the gas-phase reaction of ground-state atomic silicon (Si) with silane (SiH4) under single-collision conditions in crossed molecular beam experiments. Combined with state-of-the-art electronic structure and statistical calculations, the reaction was found to involve an initial formation of a van der Waals complex in the entrance channel, a submerged barrier to insertion, intersystem crossing (ISC) from the triplet to the singlet manifold, and hydrogen migrations. These studies provide a rare glimpse of silicon chemistry on the molecular level and shed light on the remarkable non-adiabatic reaction dynamics of silicon, which are quite distinct from those of isovalent carbon systems, providing important insight that reveals an exotic silicon chemistry to form disilavinylidene. |
| Databáze: | OpenAIRE |
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