Chemically diverse environmental interfaces and their reactions with ozone studied by sum frequency generation

Grace Y. Stokes, Avram M. Buchbinder, Julianne M. Gibbs-Davis, Karl A. Scheidt, Franz M. Geiger*

*Corresponding author for this work

Research output: Contribution to journalArticle

31 Scopus citations

Abstract

Using tailor-made organic compounds tethered to solid substrates through organo-silane chemistry, we present a reductionist model study aimed at understanding the mechanisms of heterogeneous organic oxidation reactions at solid/air interfaces. The surface vibrational spectra of glass slides functionalized with the tropospherically relevant olefins 1-pentene, 2-hexene, cyclopentene, cyclohexene, and a menthenol derivative via aniline-silane linkers have been obtained through polarization-resolved broadband vibrational sum frequency generation (SFG). The olefinic and aliphatic CH stretches located above and below 3000 cm-1, respectively, are clearly discernable and their spectral intensities are used to track, with 10 s time resolution, C{double bond, long}C double bond oxidation reactions of surface-bound cyclohexene at room temperature and with low ppm amounts of ozone at 1 atm. The olefinic CH stretching mode disappears at a rate of 0.05(1) s-1, and the aliphatic asymmetric stretch modes increase at a rate of 0.04(1) s-1. Analogous experiments show the formation of methyl groups even for those olefins under investigation that do not originally possess methyl groups. The implications for heterogeneous organic oxidation chemistry involving tropospheric dust particles are discussed.

Original languageEnglish (US)
Pages (from-to)86-98
Number of pages13
JournalVibrational Spectroscopy
Volume50
Issue number1
DOIs
StatePublished - May 26 2009

Keywords

  • Cyclohexane
  • Cyclohexene
  • Cyclopentene
  • Hexene
  • Olefins
  • Ozone
  • Pentene
  • Sum frequency generation
  • Terpene
  • Tropospheric chemistry

ASJC Scopus subject areas

  • Spectroscopy

Fingerprint Dive into the research topics of 'Chemically diverse environmental interfaces and their reactions with ozone studied by sum frequency generation'. Together they form a unique fingerprint.

  • Cite this