Reaction Dynamics Study of the Molecular Hydrogen Loss Channel in the Elementary Reactions of Ground-State Silicon Atoms (Si( 3 P)) With 1- and 2-Methyl-1,3-Butadiene (C 5 H 8 )
Reaction Dynamics Study of the Molecular Hydrogen Loss Channel in the Elementary Reactions of Ground-State Silicon Atoms (Si( 3 P)) With 1- and 2-Methyl-1,3-Butadiene (C 5 H 8 )
复制标题
基态硅原子(Si( 3 P))与1-和2-甲基-1,3-丁二烯(C 5 H 8 )基元反应中分子失氢通道的反应动力学研究
DOI：
10.1021/acs.jpca.1c03023
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Kaiser, Ralf I.
中科院分区：
文献类型：
--
作者：
Yang, Zhenghai;He, Chao;Goettl, Shane;Kaiser, Ralf I.
通过交叉分子束实验研究了基态原子硅(Si；3P)与1-和2-甲基-1，3-丁二烯的双分子气相反应。我们的数据揭示了通过长寿命的SiC5H8碰撞络合物(ES)以及分子氢损失途径的间接散射动力学，导致容易形成SiC5H6异构体(S)。我们认为硅与1-和2-甲基-1，3-丁二烯的反应具有类似于硅-1，3-丁二烯体系的反应动力学。这导致环甲基取代的2-亚甲基-1-硅环丁烯异构体通过非绝热反应动力学从三重态跨越到单重态表面，通过紧密的出射过渡态和分子氢损失在整个外能反应中得到。我们的研究还表明，甲基--尽管从化学观点来看是旁观者--可以影响角动量的处理，使其转化为最终产物的旋转激发。
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 SiC5H8collision complex(es) along with molecular hydrogen loss pathways, leading to facile formation of SiC5H6isomer(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.