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Competing Mechanisms in the Acetaldehyde Functionalization of Positively Charged Hydrogenated Silicene
Author(s) -
Yang LiKun,
Zhang XiaGuang,
Yang FangZu,
Wu DeYin,
Liu XiangYang,
Tian ZhongQun
Publication year - 2017
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201601013
Subject(s) - silicene , dangling bond , density functional theory , chemical physics , chemistry , computational chemistry , hydrogen atom abstraction , silicon , hydrogen , materials science , organic chemistry
Density functional theory calculations were used to elucidate the mechanism of the addition reaction of acetaldehyde to positively charged hydrogenated silicene (H‐silicene). We found that the positively charged H‐silicene plane could be partially restructured to form a vacant Si site, which enabled an additional nucleophilic addition reaction. After attachment of the acetaldehyde molecule to the H‐silicene plane, two competing pathways were found to be involved in the hydrogen‐abstraction process: a random‐reaction mechanism and a chain‐reaction mechanism. The theoretical results provided detailed information about stable structures and thermodynamic parameters of the reaction pathways, such as equilibrium geometries, Gibbs free energies, and the evolution of the spin densities and atomic charges. Our results reveal that the existence of a positive charge can significantly activate the grafting of unsaturated species on hydrogenated silicene, even if no silicon dangling bond is created proactively. The simulated Raman spectra of the two products were analyzed to elucidate the features of the competing mechanisms.