We report direct experimental and theoretical evidence that, under single-collision conditions, the dominant product channels of the O(3P) + propyne and O(3P) + allene isomeric reactions lead in both cases to CO formation, but the coproducts are singlet ethylidene (1CH3CH) and singlet ethylene (CH2CH2), respectively. These data, which settle a long-standing issue on whether ethylidene is actually formed in the O(3P) + propyne reaction, suggest that formation of CO + alkylidene biradicals may be a common mechanism in O(3P) + alkyne reactions, in contrast to formation of CO + alkene molecular products in the corresponding isomeric O(3P) + diene reactions, either in combustion or other gaseous environments. These findings are of fundamental relevance and may have implications for improved combustion models. Moreover, we predict that the so far neglected 1CH3CH + CO channel is among the main reaction routes also when the C3H4O singlet potential energy surface is accessed from the OH + C3H3 (propargyl) entrance channel, which are radical species playing a key role in many combustion systems.

Isomer-Specific Chemistry in the Propyne and Allene Reactions with Oxygen Atoms: CH3CH + CO versus CH2CH2 + CO Products

GIMONDI, ILARIA;CAVALLOTTI, CARLO ALESSANDRO
2016-01-01

Abstract

We report direct experimental and theoretical evidence that, under single-collision conditions, the dominant product channels of the O(3P) + propyne and O(3P) + allene isomeric reactions lead in both cases to CO formation, but the coproducts are singlet ethylidene (1CH3CH) and singlet ethylene (CH2CH2), respectively. These data, which settle a long-standing issue on whether ethylidene is actually formed in the O(3P) + propyne reaction, suggest that formation of CO + alkylidene biradicals may be a common mechanism in O(3P) + alkyne reactions, in contrast to formation of CO + alkene molecular products in the corresponding isomeric O(3P) + diene reactions, either in combustion or other gaseous environments. These findings are of fundamental relevance and may have implications for improved combustion models. Moreover, we predict that the so far neglected 1CH3CH + CO channel is among the main reaction routes also when the C3H4O singlet potential energy surface is accessed from the OH + C3H3 (propargyl) entrance channel, which are radical species playing a key role in many combustion systems.
2016
Materials Science (all)
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11311/1013150
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