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    Publication Date: 2014-09-27
    Description: Ozonolysis of alkenes, an important nonphotolytic source of hydroxyl (OH) radicals in the troposphere, proceeds through energized Criegee intermediates that undergo unimolecular decay to produce OH radicals. Here, we used infrared (IR) activation of cold CH3CHOO Criegee intermediates to drive hydrogen transfer from the methyl group to the terminal oxygen, followed by dissociation to OH radicals. State-selective excitation of CH3CHOO in the CH stretch overtone region combined with sensitive OH detection revealed the IR spectrum of CH3CHOO, effective barrier height for the critical hydrogen transfer step, and rapid decay dynamics to OH products. Complementary theory provides insights on the IR overtone spectrum, as well as vibrational excitations, structural changes, and energy required to move from the minimum-energy configuration of CH3CHOO to the transition state for the hydrogen transfer reaction.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Liu, Fang -- Beames, Joseph M -- Petit, Andrew S -- McCoy, Anne B -- Lester, Marsha I -- New York, N.Y. -- Science. 2014 Sep 26;345(6204):1596-8. doi: 10.1126/science.1257158.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323, USA. ; Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH 43210-1173, USA. ; Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323, USA. milester@sas.upenn.edu.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/25258077" target="_blank"〉PubMed〈/a〉
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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