Density functional study of the adsorption of 1,4-cyclohexadiene on Pt(1 1 1): Origin of the C-H stretch red shift

Mark Saeys, Marie Françoise Reyniers, Guy B. Marin, Matthew Neurock

Research output: Contribution to journalArticle

27 Scopus citations

Abstract

The adsorption of 1,4-cyclohexadiene (CHD14) on Pt(1 1 1) was analysed using first-principle density functional theoretical calculations. CHD14 adsorbs at the bridge site via quadra-σ-type bonding. The adsorption energy was calculated to be 146 kJ/mol. CHD14 can also adsorb at the hollow site via the formation of a di-σ- and a π-bond with an adsorption energy of 142 kJ/mol. Upon adsorption CHD14 adopts a boat conformation. Strong π-electron donation to the platinum surface in combination with a hyperconjugative interaction of these π-orbitals with the axial σCH orbital helps to explain the observed red shift of the axial C-H stretching frequency and the corresponding C-H bond lengthening.

Original languageEnglish (US)
Pages (from-to)315-327
Number of pages13
JournalSurface Science
Volume513
Issue number2
DOIs
StatePublished - Jul 1 2002

Keywords

  • Alkenes
  • Aromatics
  • Chemisorption
  • Density functional calculations
  • Low index single crystal surfaces
  • Models of surface chemical reactions
  • Platinum
  • Single crystal surfaces
  • Vibrations of adsorbed molecules

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