Efficient subpicosecond photoinduced surface chemistry

The ultrafast photooxidation of CO on palladium

P. Szymanski, Alex Harris, N. Camillone

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Ultrafast near-infrared photoexcitation of mixed adlayers of carbon monoxide and atomic oxygen on the Pd(111) surface results in the efficient associative desorption of carbon dioxide. The oxidized fraction of the desorbed molecules ranges from ∼15% to 40%, approximately an order of magnitude greater than observed from Ru(001) under similar conditions. Time-resolved correlation measurements reveal fast dynamics that indicate the photochemistry is mediated by substrate electrons. The dynamics are strongly dependent on the initial CO coverage in a manner consistent with an activation energy for oxidation that depends on the initial CO binding site. These results, in addition to comparison of the ultrafast photooxidation to thermal oxidation, are consistent with the photooxidation occurring rapidly (within one to several picoseconds) from an initial mixed CO+O adlayer structure without time for diffusional phase segregation. The observed efficient ultrafast photoexcitation of associative desorption of CO2 from Pd(111) thus provides the opportunity to follow the picosecond dynamics of the bimolecular surface chemical reaction of CO+O from a well-defined initial geometry.

Original languageEnglish
Pages (from-to)15802-15808
Number of pages7
JournalJournal of Physical Chemistry C
Volume112
Issue number40
DOIs
Publication statusPublished - Oct 9 2008

Fingerprint

Photooxidation
photooxidation
Palladium
Carbon Monoxide
Surface chemistry
palladium
Photoexcitation
chemistry
photoexcitation
Desorption
desorption
Oxidation
oxidation
Photochemical reactions
Binding sites
Carbon monoxide
photochemical reactions
carbon monoxide
carbon dioxide
Chemical reactions

ASJC Scopus subject areas

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

Cite this

Efficient subpicosecond photoinduced surface chemistry : The ultrafast photooxidation of CO on palladium. / Szymanski, P.; Harris, Alex; Camillone, N.

In: Journal of Physical Chemistry C, Vol. 112, No. 40, 09.10.2008, p. 15802-15808.

Research output: Contribution to journalArticle

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