Issue 24, 2005

A matrix isolation study of the Cs symmetric OCNO(X 2A″) radical

Abstract

Here we report the first experimental detection of the Cs symmetric nitroformyl radical, OCNO(X 2A″) in a nitrogen–carbon dioxide matrix at 10 K using a Fourier transform infrared spectrometer (FTIR). The ν1 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).

Graphical abstract: A matrix isolation study of the Cs symmetric OCNO(X 2A″) radical

Article information

Article type
Paper
Submitted
23 Aug 2005
Accepted
27 Sep 2005
First published
14 Oct 2005

Phys. Chem. Chem. Phys., 2005,7, 4089-4095

A matrix isolation study of the Cs symmetric OCNO(X 2A″) radical

C. S. Jamieson, A. M. Mebel and R. I. Kaiser, Phys. Chem. Chem. Phys., 2005, 7, 4089 DOI: 10.1039/B511978B

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