title: Gas-Phase Formation of the Disilavinylidene (H2SiSi) Transient.
abstract: 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.
authors.affiliation: Department of Chemistry, University of Hawai'i at Manoa, Honolulu, HI, 96822, USA.
authors.forename: Tao
authors.identifier: 0000-0003-4101-2385
authors.initials: T
authors.lastname: Yang
authors.affiliation: Department of Chemistry, University of Hawai'i at Manoa, Honolulu, HI, 96822, USA.|Department of Chemistry, Florida A&M University, Tallahassee, FL, 32307, USA.
authors.forename: Beni B
authors.initials: BB
authors.lastname: Dangi
authors.affiliation: Department of Chemistry, University of Hawai'i at Manoa, Honolulu, HI, 96822, USA.
authors.forename: Ralf I
authors.identifier: 0000-0002-7233-7206
authors.initials: RI
authors.lastname: Kaiser
authors.affiliation: Department of Chemistry, National Dong Hwa University, Shoufeng, Hualien, 974, Taiwan.
authors.forename: Kang-Heng
authors.initials: KH
authors.lastname: Chao
authors.affiliation: Department of Chemistry, National Dong Hwa University, Shoufeng, Hualien, 974, Taiwan.
authors.forename: Bing-Jian
authors.initials: BJ
authors.lastname: Sun
authors.affiliation: Department of Chemistry, National Dong Hwa University, Shoufeng, Hualien, 974, Taiwan.
authors.forename: Agnes H H
authors.initials: AH
authors.lastname: Chang
authors.affiliation: Department of Chemistry, University of Texas at Austin, Austin, TX, 78712, USA.
authors.forename: Thanh Lam
authors.initials: TL
authors.lastname: Nguyen
authors.affiliation: Department of Chemistry, University of Texas at Austin, Austin, TX, 78712, USA.
authors.forename: John F
authors.initials: JF
authors.lastname: Stanton
keywords: gas-phase chemistry; mass spectrometry; reaction dynamics; silicon; single-collision conditions