40min:

BARNEY ELLISON, Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309-0215.

Complex organic radicals are important intermediates in many combustion and environmental processes. In combustion processes, the organic radical CH is known to cleave N₂ into HCN and N atoms. Most N atoms are further oxidized to NO which exhausts into the atmosphere. Thus the reaction of CH with N₂ to produce N atoms connects internal combustion engines with NO production. Some fraction of these N atoms, however, reacts with CH₃ in the flame to produce CH₃N. Methylnitrene is very unstable and decomposes to generate CH₂NH or H₂ + HCN. We will discuss the use of negative ion photoelectron spectroscopy to characterize methylnitrene.

\begineqnarray CH₃N^- + \hbar _488~nm CH₃N+e^- \nonumber \endeqnarray We find EA(CH₃N) = 0.022 \pm 0.009 eV. In addition to detaching the methylnitrene anion to the ground state of CH₃N (X~³A₂), we also detect the first electronically excited state of methylnitrene, a ¹E. We measure E(a ¹E- X ³A₂) = 1.352 \pm 0.011 eV. The reaction dynamics of nitrene rearrangements will be discussed:

\begineqnarray CH₃ N (X~³\textrmA₂) \textrmno reaction\nonumber
CH₃ N (a ¹\textrmE) CH₂ NH \nonumber \endeqnarray