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THE ROLE OF A NOVEL DIRADICAL PATHWAY IN REACTIONS BETWEEN PEROXYL RADICALS AND NO

Please use this identifier to cite or link to this item: http://hdl.handle.net/1811/21028

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Title: THE ROLE OF A NOVEL DIRADICAL PATHWAY IN REACTIONS BETWEEN PEROXYL RADICALS AND NO
Creators: Jochnowitz, Evan B.; Blanksby, Stephen J.; Ellison, G. B.; Stanton, John F.
Issue Date: 2003
Abstract: The conversion of peroxyl radicals to organic nitrates via reaction with NO is of importance in atmospheric chemistry and biochemistry. The mechanism for nitrate formation is obscure; no previous theoretical results have been even vaguely consistent with the experimental evidence. We propose a simple valence bond argument to rationalize how an initially formed pernitrite, ROONO, can decompose to an alkoxy radical and $NO_{2}$ or rearrange to $RONO_{2}$. This qualitative mechanism, which involves the coupling of two valence bond states, is supported by coupled-cluster electronic structure calculations that predict a barrier of ca. 20-30 kcal $mol^{-1}$, that is provided by the radical/radical adduct. In addition to its obvious importance for atmospheric chemistry, it is likely that this mechanism is also responsible for chain termination of the oxygen-dependent oxidation of lipid membranes in biological cells. The mechanism can likewise be applied to the thermal decomposition of organic nitro compounds (explosives and solid propellants), $RNO_{2} + heat \rightarrow$ products.
URI: http://hdl.handle.net/1811/21028
Other Identifiers: 2003-TG-06
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