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

Junwei Lucas Bao, Donald G. Truhlar

Research output: Contribution to journalArticlepeer-review

23 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)10097-10108
Number of pages12
JournalPhysical Chemistry Chemical Physics
Volume18
Issue number15
DOIs
StatePublished - Apr 21 2016

Bibliographical note

Funding Information:
The authors appreciate helpful discussion with Steven L. Girshick and Mark J. Kushner and valuable contributions from Prasenjit Seal. This work is supported by the National Science Foundation under award no. CHE11-24752.

Publisher Copyright:
© the Owner Societies 2016.

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