Journal
NATURE CHEMISTRY
Volume 9, Issue 11, Pages 1078-1082Publisher
NATURE PUBLISHING GROUP
DOI: 10.1038/nchem.2842
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Funding
- US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences [DE-AC02-06CH11357]
- Columbia University
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Termolecular association reactions involve ephemeral collision complexes-formed from the collision of two molecules that collide with a third and chemically inert 'bath gas' molecule that simply transfers energy to/from the complex. These collision complexes are generally not thought to react chemically on collision with a third molecule in the gas-phase systems of combustion and planetary atmospheres. Such 'chemically termolecular' reactions, in which all three molecules are involved in bond making and/or breaking, were hypothesized long ago in studies establishing radical chain branching mechanisms, but were later concluded to be unimportant. Here, with data from ab initio master equation and kinetic-transport simulations, we reveal that reactions of H + O-2 collision complexes with other radicals constitute major kinetic pathways under common combustion situations. These reactions are also found to influence flame propagation speeds, a common measure of global reactivity. Analogous chemically termolecular reactions mediated by ephemeral collision complexes are probably of significance in various combustion and planetary environments.
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