A matrix isolation study of the C(s) symmetric OCNO(X 2A'') radical

Phys Chem Chem Phys. 2005 Dec 21;7(24):4089-95. doi: 10.1039/b511978b. Epub 2005 Oct 14.


Here we report the first experimental detection of the C(s) symmetric nitroformyl radical, OCNO(X 2A'') in a nitrogen-carbon dioxide matrix at 10 K using a Fourier transform infrared spectrometer (FTIR). The nu1 vibrational frequency was observed at 2113 cm(-1). This assignment was confirmed by follow-up experiments using isotopically labeled reactant molecules (15N, 18O, 13C). To synthesize this radical, we irradiated solid nitrogen-carbon dioxide ice mixtures with energetic electrons at 10 K. Suprathermal nitrogen atoms in their electronic ground and/or first electronically excited state were generated via the radiation induced degradation of molecular nitrogen; these atoms could then react with carbon dioxide to eventually yield the nitroformyl radical. We also investigated the kinetics of the formation of the nitroformyl radical and support the arguments with computations on the doublet and quartet OCNO potential energy surfaces (PESs).

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Carbon Dioxide / chemistry*
  • Cold Temperature
  • Electrons
  • Free Radicals / chemical synthesis
  • Free Radicals / chemistry
  • Kinetics
  • Nitrogen / chemistry*
  • Spectroscopy, Fourier Transform Infrared
  • Vibration


  • Free Radicals
  • Carbon Dioxide
  • Nitrogen