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

摘要: Bimolecular reactions in Earth’s atmosphere are generally assumed to proceed between reactants whose internal quantum states fully thermally relaxed. Here, we highlight a dramatic role for vibrationally excited bimolecular the oxidation of acetylene. The reaction proceeds by preliminary adduct formation alkyne and OH radical, with subsequent O2 addition. Using detailed theoretical model, show that product-branching ratio is determined vibrational quantum-state distribution at moment it reacts O2. Experimentally, found under simulated atmospheric conditions intercepts ~25% adducts before their have Analogous interception excited-state radicals likely common range through peroxy complexes.