Role of molecular conjugation in the surface radical reaction of aldehydes with H-Si(111): First principles study

Yosuke Kanai, Noboru Takeuchi, Roberto Car, Annabella Selloni

Research output: Contribution to journalArticle

30 Scopus citations

Abstract

Within the current effort to understand and develop the organic functionalization of silicon surfaces, recent experiments have identified the radical chain reaction of unsaturated organic molecules with H-terminated silicon surfaces as a particularly promising route for controlled formation of such functionalized surfaces. Using periodic density functional theory calculations, we theoretically study and characterize the basic steps of the radical chain reaction mechanism for different aldehyde molecules (formaldehyde, benzaldehyde, propanaldehyde, propenaldehyde) reacting with the H-Si(111) surface, under the assumption that a Si dangling bond is initially present on the surface. Molecular conjugation is found to play a crucial role in the viability of the reaction, by controlling the delocalization of the spin density at the reaction intermediate. Interesting differences between our present results for aldehydes and our previous study for the reactions of alkene/alkyne molecules with H-Si(111) are observed and discussed (Takeuchi et al. J. Am. Chem. Soc. 2004, 126, 15890).

Original languageEnglish (US)
Pages (from-to)18889-18894
Number of pages6
JournalJournal of Physical Chemistry B
Volume109
Issue number40
DOIs
StatePublished - Oct 13 2005

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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