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      Interception of excited vibrational quantum states by O2 in atmospheric association reactions.

      Science (New York, N.Y.)
      Acetylene, chemistry, Atmosphere, Models, Chemical, Oxidation-Reduction, Oxygen, Quantum Theory, Vibration

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          Abstract

          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 ~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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          Author and article information

          Journal
          22936771
          10.1126/science.1224106

          Chemistry
          Acetylene,chemistry,Atmosphere,Models, Chemical,Oxidation-Reduction,Oxygen,Quantum Theory,Vibration
          Chemistry
          Acetylene, chemistry, Atmosphere, Models, Chemical, Oxidation-Reduction, Oxygen, Quantum Theory, Vibration

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