Issue 24, 2015

Nanodusty plasma chemistry: a mechanistic and variational transition state theory study of the initial steps of silyl anion–silane and silylene anion–silane polymerization reactions

Abstract

The growth of nanodusty particles, which is critical in plasma chemistry, physics, and engineering. The aim of the present work is to understand the detailed reaction mechanisms of early steps in this growth. The polymerization of neutral silane with the silylene or silyl anion, which eliminates molecular hydrogen with the formation of their higher homologues, governs the silicon hydride clustering in nanodusty plasma chemistry. The detailed mechanisms of these important polymerization reactions in terms of elementary reactions have not been proposed yet. In the present work, we investigated the initial steps of these polymerization reactions, i.e., the SiH4 + Si2H4/Si2H5 reactions, and we propose a three-step mechanism, which is also applicable to the following polymerization steps. CM5 charges of all the silicon-containing species were computed in order to analyze the character of the species in the proposed reaction mechanisms. We also calculated thermal rate constant of each step using multi-structural canonical variational transition state theory (MS-CVT) with the small-curvature tunneling (SCT) approximation, based on the minimum energy path computed using M08-HX/MG3S electronic structure method.

Graphical abstract: Nanodusty plasma chemistry: a mechanistic and variational transition state theory study of the initial steps of silyl anion–silane and silylene anion–silane polymerization reactions

Supplementary files

Article information

Article type
Paper
Submitted
05 Apr 2015
Accepted
18 May 2015
First published
18 May 2015
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2015,17, 15928-15935

Nanodusty plasma chemistry: a mechanistic and variational transition state theory study of the initial steps of silyl anion–silane and silylene anion–silane polymerization reactions

J. L. Bao, P. Seal and D. G. Truhlar, Phys. Chem. Chem. Phys., 2015, 17, 15928 DOI: 10.1039/C5CP01979F

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