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Gas‐Phase Formation of the Disilavinylidene (H 2 SiSi) Transient
Author(s) -
Yang Tao,
Dangi Beni B.,
Kaiser Ralf I.,
Chao KangHeng,
Sun BingJian,
Chang Agnes H. H.,
Nguyen Thanh Lam,
Stanton John F.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201611107
Subject(s) - intersystem crossing , silicon , crossed molecular beam , chemistry , van der waals force , silane , singlet state , photochemistry , ground state , chemical physics , molecule , gas phase , hydrogen , computational chemistry , atomic physics , excited state , physics , organic chemistry
The hitherto elusive disilavinylidene (H 2 SiSi) molecule, which is in equilibrium with the mono‐bridged (Si(H)SiH) and di‐bridged (Si(H 2 )Si) isomers, was initially formed in the gas‐phase reaction of ground‐state atomic silicon (Si) with silane (SiH 4 ) 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.