Direct observation of the gas-phase Criegee intermediate (CH2OO).

Combustion Research Facility, Mail Stop 9055, Sandia National Laboratories, Livermore, California 94551-0969, USA.
Journal of the American Chemical Society (Impact Factor: 10.68). 10/2008; 130(36):11883-5. DOI: 10.1021/ja804165q
Source: PubMed

ABSTRACT Carbonyl oxide species play a key role in tropospheric oxidation of organic molecules and in low-temperature combustion processes. In the late 1940s, Criegee first postulated the participation of carbonyl oxides, now often called "Criegee intermediates," in ozonolysis of alkenes. However, despite decades of effort, no gas phase Criegee intermediate has before been observed. As a result, knowledge of gas phase carbonyl oxide reactions has heretofore been inferred by indirect means, with derived rate coefficients spanning orders of magnitude. We have directly detected the primary Criegee intermediate, formaldehyde oxide (CH2OO), in the chlorine-initiated gas-phase oxidation of dimethyl sulfoxide (DMSO). This work not only establishes that the Criegee intermediate is formed in DMSO oxidation also but opens the possibility for explicit kinetics studies on this critical atmospheric species.

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    ABSTRACT: The UV spectrum of CH3CHOO was measured by transient absorption in a flow cell at 295 K. The absolute absorption cross sections of CH3CHOO were measured by laser depletion in a molecular beam to be (1.06 ± 0.09) × 10(-17) cm(2) molecule(-1) at 308 nm and (9.7 ± 0.6) × 10(-18) cm(2) molecule(-1) at 352 nm. After scaling the UV spectrum of CH3CHOO to the absolute cross section at 308 nm, the peak UV cross section is (1.27 ± 0.11) × 10(-17) cm(2) molecule(-1) at 328 nm. Compared to the simplest Criegee intermediate CH2OO, the UV absorption band of CH3CHOO is similar in intensity but blue shifted by 14 nm, resulting in a 20% slower photolysis rate estimated for CH3CHOO in the atmosphere.
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    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 (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 2H2CO + O2((1)Δg). 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.
    Nature Chemistry 06/2014; 6(6):477-83. · 21.76 Impact Factor
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    ABSTRACT: A new model, BAMBO (Bristol's Atmospheric Marine Boundary layer mOdel), was developed in order to investigate the reaction between peroxy radicals (RO2) and the hydroxyl radical (OH) under typical marine boundary layer (MBL) conditions. The results of this work have shown that the inclusion of the title reaction has negligible effects on inorganic species and ozone but can have significant effects on predicted atmospheric mixing ratios of oxygenated volatile organic compounds (OVOCs), which are generally poorly represented in atmospheric models. This work highlights that the title reaction may be important to modelling trace gas composition in the MBL. However, thorough experimental and theoretical studies are needed to clarify many of the assumptions made. Copyright © 2009 Royal Meteorological Society
    Atmospheric Science Letters 04/2009; 10(2). · 1.75 Impact Factor