Effects of radical site location and surface doping on the radical chain-reaction on H-Si(100)-(2 × 1): A density functional theory study

Yong Pei, Jing Ma, Xiao Cheng Zeng

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

The radical chain-reactions of allyl mercaptan, ethylene oxide, propylene oxide, and 1,3-butadiene molecules on the H-Si(100)-(2 × 1) are systematically investigated on the basis of a hybrid (ONIOM) model. The formation of γC-, δC-, or δS-site radical intermediate reduces the kinetic selectivity of H-abstraction reactions. The H-abstraction activation energies have the order of across dimer row < interdimer (in the same dimer row) < intradimer H-abstraction, contrasting to the previously reported tendency of βC-site radical intermediate. The steric factor greatly affects the direction-selectivity of radical chain-reaction. The discrepancy between chain-reaction of allyl mercaptan [J. Am. Chem. Soc. 2007, 729, 12304] and trimethylene sulfide molecules [J. Phys. Chem. C 2007, 111, 11965] is rationalized by the doping effect of silicon substrate. It suggests the doping of silicon substrate can alter the direction of the surface chain-reaction. Furthermore, we also theoretically predict the self-directed growth behaviors of ethylene oxide, propylene oxide, and 1,3-butadiene molecules on the H-Si(100)-(2 × 1). The predicted growth behavior of 1,3-butadiene molecules is in good agreement with recent experimental observations.

Original languageEnglish (US)
Pages (from-to)16078-16086
Number of pages9
JournalJournal of Physical Chemistry C
Volume112
Issue number41
DOIs
StatePublished - Oct 16 2008

Fingerprint

Density functional theory
Butadiene
Doping (additives)
density functional theory
Ethylene Oxide
butadiene
Molecules
Oxides
Silicon
Sulfhydryl Compounds
propylene oxide
Dimers
Propylene
ethylene oxide
Ethylene
thiols
molecules
selectivity
dimers
Sulfides

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Effects of radical site location and surface doping on the radical chain-reaction on H-Si(100)-(2 × 1) : A density functional theory study. / Pei, Yong; Ma, Jing; Zeng, Xiao Cheng.

In: Journal of Physical Chemistry C, Vol. 112, No. 41, 16.10.2008, p. 16078-16086.

Research output: Contribution to journalArticle

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