Sequential clustering reactions of Si+ with silane: A theoretical study of the reaction mechanisms
Sequential clustering reactions of Si+ with silane: A theoretical study of the reaction mechanisms
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Si 与硅烷的连续簇化反应：反应机理的理论研究
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发表时间：
1988
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通讯作者：
K. Raghavachari
中科院分区：
文献类型：
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作者：
K. Raghavachari
通过精确的量子化学技术，使用极化基组，并包括电子相关和零点修正的影响，研究了Si+与SiH 4的顺序簇合反应的机制。根据Mandich，Reents和Jarrold的实验结果，反应导致形成Si 2 H +2，SiH+4，Si 4 H +6，最后是Si 5 H +10。详细的反应途径，包括必要的过渡结构的研究导致在每个反应步骤中的特定异构体的产品的分配。指定的特定异构体为H2Si-Si+、H3 Si-SiH-Si+、（H3 Si）2Si-Si+和（H3 Si）3Si-SiH+。反应顺序中的瓶颈是由于支化产物Si 5 H +10的形成，其中由于涉及中心硅原子的键合的饱和而不容易消除H2。同位素交换反应，已经看到实验上也合理化的这一机制。定量比较是…
The mechanisms of the sequential clustering reactions of Si+ with SiH4 have been studied by means of accurate quantum chemical techniques using polarized basis sets and including the effects of electron correlation and zero‐point corrections. In accordance with the experimental results of Mandich, Reents, and Jarrold, the reactions lead to the formation of Si2H+2, SiH+4, Si4H+6, and finally Si5H+10. The study of the detailed reaction pathways including the necessary transition structures leads to the assignment of specific isomeric products in each reaction step. The specific isomers assigned are H2Si–Si+, H3Si–SiH–Si+, (H3Si)2Si–Si+, and (H3Si)3Si–SiH+. The bottleneck in the reaction sequence is due to the formation of the branched product Si5H+10 where elimination of H2 is not easily possible due to the saturation of the bonding involving the central silicon atom. Isotopic exchange reactions which have been seen experimentally are also rationalized by this mechanism. Quantitative comparisons are made be...