Extremely rapid self-reaction of the simplest Criegee intermediate CH 2 OO and its implications in atmospheric chemistry

Yu Te Su, Hui Yu Lin, Raghunath Putikam, Hiroyuki Matsui, Ming-Chang Lin, Yuan-Pern Lee*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

87 Scopus citations

Abstract

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 (CH 2 OO) 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 CH 2 OO bonded to the C atom of the other CH 2 OO is formed with large exothermicity before further decomposition to 2H 2 CO + O 2 (1 Δ 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.

Original languageEnglish
Pages (from-to)477-483
Number of pages7
JournalNature Chemistry
Volume6
Issue number6
DOIs
StatePublished - 23 Mar 2014

Fingerprint Dive into the research topics of 'Extremely rapid self-reaction of the simplest Criegee intermediate CH 2 OO and its implications in atmospheric chemistry'. Together they form a unique fingerprint.

Cite this