气候变化领域集成服务门户(CCPortal): Interception of excited vibrational quantum states by O2 in atmospheric association reactions

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DOI	10.1126/science.1224106
	Interception of excited vibrational quantum states by O2 in atmospheric association reactions
	Glowacki D.R.; Lockhart J.; Blitz M.A.; Klippenstein S.J.; Pilling M.J.; Robertson S.H.; Seakins P.W.
发表日期	2012
ISSN	0036-8075
起始页码	1066
结束页码	1069
卷号	337 期号:6098
英文摘要	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 O2 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 O2. 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 O2 is likely common to a range of atmospheric reactions that proceed through peroxy complexes.
英文关键词	acetylene; alkyne; oxygen; peroxy radical; acetylene; atmospheric chemistry; atmospheric modeling; hydroxide; interception; molecular analysis; oxygen; quantum mechanics; radical; temperature effect; theoretical study; air temperature; article; atmospheric pressure; excitation; gas; kinetics; oxidation; photolysis; priority journal; quantum chemistry; room temperature; simulation; stochastic model; theoretical model; thermodynamics; vibration
语种	英语
来源期刊	Science
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/243819
作者单位	School of Chemistry, University of Bristol, Bristol BS8 1TS, United Kingdom; School of Chemistry, University of Leeds, Leeds LS2 9JT, United Kingdom; Argonne National Laboratory, Chemical Sciences and Engineering Division, Argonne, IL 60439, United States; Accelrys, 334 Cambridge Science Park, Cambridge CB4 0WN, United Kingdom
推荐引用方式 GB/T 7714	Glowacki D.R.,Lockhart J.,Blitz M.A.,et al. Interception of excited vibrational quantum states by O2 in atmospheric association reactions[J],2012,337(6098).
APA	Glowacki D.R..,Lockhart J..,Blitz M.A..,Klippenstein S.J..,Pilling M.J..,...&Seakins P.W..(2012).Interception of excited vibrational quantum states by O2 in atmospheric association reactions.Science,337(6098).
MLA	Glowacki D.R.,et al."Interception of excited vibrational quantum states by O2 in atmospheric association reactions".Science 337.6098(2012).