Issue 15, 2016

Silane-initiated nucleation in chemically active plasmas: validation of density functionals, mechanisms, and pressure-dependent variational transition state calculations

Abstract

The growth of anionic silicon hydride clusters is a critically important process in nanodusty plasmas. In the current study, we focus on the formation of homologs of silylene (Sin+1H2n+2, n = 3, 4) and silyl (SinH2n+1, n = 4, 5) anions via anion–neutral reaction pathways. Species like silyl or silylene anions and their related elementary reactions, which are involved in the formation of silicon hydride clusters, were not used in developing exchange–correlation (xc) density functionals (i.e., they were not included in the training set of semiempirical density functionals); therefore, we explored the accuracy of various widely used xc density functionals based on reaction energies and barrier heights. Among the 21 density functionals we tested, M06-2X has the best performance for a hybrid functional, and MN15-L has the best performance for a local functional. Thermal rate constants of the elementary reactions involved in the reaction mechanism are calculated using M06-2X and multistructural canonical variational transition state theory with the small-curvature tunneling approximation (MS-CVT/SCT). The pressure dependence of unimolecular isomerization reactions is treated with system-specific quantum RRK theory (SS-QRRK) and the Lindemann–Hinshelwood mechanism.

Graphical abstract: Silane-initiated nucleation in chemically active plasmas: validation of density functionals, mechanisms, and pressure-dependent variational transition state calculations

Supplementary files

Article information

Article type
Paper
Submitted
05 Feb 2016
Accepted
10 Mar 2016
First published
11 Mar 2016
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2016,18, 10097-10108

Silane-initiated nucleation in chemically active plasmas: validation of density functionals, mechanisms, and pressure-dependent variational transition state calculations

J. L. Bao and D. G. Truhlar, Phys. Chem. Chem. Phys., 2016, 18, 10097 DOI: 10.1039/C6CP00816J

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements