Journal
SCIENCE
Volume 337, Issue 6098, Pages 1066-1069Publisher
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.1224106
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Funding
- Engineering and Physical Sciences Research Council [EP/G00224X]
- Natural Environment Research Council via the National Centre for Atmospheric Science
- U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences [DE-AC02-06CH11357]
- [NE/F018754/1]
- Engineering and Physical Sciences Research Council [EP/J010871/1] Funding Source: researchfish
- Natural Environment Research Council [ncas10006, NE/F018754/1] Funding Source: researchfish
- EPSRC [EP/J010871/1] Funding Source: UKRI
- NERC [NE/F018754/1, ncas10006] Funding Source: UKRI
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Bimolecular reactions in Earth's atmosphere are generally assumed to proceed between reactants whose internal quantum states are fully thermally relaxed. Here, we highlight a dramatic role for vibrationally excited bimolecular reactants in the oxidation of acetylene. The reaction proceeds by preliminary adduct formation between the alkyne and OH radical, with subsequent O-2 addition. Using a detailed theoretical model, we show that the product-branching ratio is determined by the excited vibrational quantum-state distribution of the adduct at the moment it reacts with O-2. Experimentally, we found that under the simulated atmospheric conditions O-2 intercepts similar to 25% of the excited adducts before their vibrational quantum states have fully relaxed. Analogous interception of excited-state radicals by O-2 is likely common to a range of atmospheric reactions that proceed through peroxy complexes.
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