標題: Extremely rapid self-reaction of the simplest Criegee intermediate CH2OO and its implications in atmospheric chemistry
作者: Su, Yu-Te
Lin, Hui-Yu
Putikam, Raghunath
Matsui, Hiroyuki
Lin, M. C.
Lee, Yuan-Pern
應用化學系
應用化學系分子科學碩博班
Department of Applied Chemistry
Institute of Molecular science
公開日期: 1-六月-2014
摘要: Criegee intermediates, which are carbonyl oxides produced when ozone reacts with unsaturated hydrocarbons, play an important role in the formation of OH and organic acids in the atmosphere, but they have eluded direct detection until recently. Reactions that involve Criegee intermediates are not understood fully because data based on their direct observation are limited. We used transient infrared absorption spectroscopy to probe directly the decay kinetics of formaldehyde oxide (CH2OO) and found that it reacts with itself extremely rapidly. This fast self-reaction is a result of its zwitterionic character. According to our quantum-chemical calculations, a cyclic dimeric intermediate that has the terminal O atom of one CH2OO bonded to the C atom of the other CH2OO is formed with large exothermicity before further decomposition to 2H(2)CO + O-2 ((1)Delta(g)). We suggest that the inclusion of this previously overlooked rapid reaction in models may affect the interpretation of previous laboratory experiments that involve Criegee intermediates.
URI: http://dx.doi.org/10.1038/NCHEM.1890
http://hdl.handle.net/11536/24703
ISSN: 1755-4330
DOI: 10.1038/NCHEM.1890
期刊: NATURE CHEMISTRY
Volume: 6
Issue: 6
起始頁: 477
結束頁: 483
顯示於類別:期刊論文