Products of Criegee intermediate reactions with NO2: experimental measurements and tropospheric implications

被引:44
作者
Caravan, Rebecca L. [1 ]
Khan, M. Anwar H. [2 ]
Rotavera, Brandon [1 ]
Papajak, Ewa [1 ]
Antonov, Ivan O. [1 ]
Chen, Ming-Wei [1 ]
Au, Kendrew [1 ]
Chao, Wen [3 ,4 ]
Osborn, David L. [1 ]
Lin, Jim Jr-Min [3 ,4 ]
Percival, Carl J. [5 ]
Shallcrossb, Dudley E. [2 ]
Taatjes, Craig A. [1 ]
机构
[1] Sandia Natl Labs, Combust Res Facil, Mailstop 9055, Livermore, CA 94551 USA
[2] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England
[3] Acad Sinica, Inst Atom & Mol Sci, Taipei 10617, Taiwan
[4] Natl Taiwan Univ, Dept Chem, Taipei 10617, Taiwan
[5] Univ Manchester, Sch Earth Atmospher & Environm Sci, Williamson Bldg,Oxford Rd, Manchester M13 9PL, Lancs, England
关键词
RESOLVED MASS-SPECTROMETRY; CORRELATED WAVE-FUNCTIONS; GAS-PHASE REACTIONS; CRI MECHANISM; BASIS-SETS; KINETICS MEASUREMENTS; WATER-VAPOR; CHEMISTRY; CH2OO; ATMOSPHERE;
D O I
10.1039/c7fd00007c
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The reactions of Criegee intermediates with NO2 have been proposed as a potentially significant source of the important nighttime oxidant NO3, particularly in urban environments where concentrations of ozone, alkenes and NOx are high. However, previous efforts to characterize the yield of NO3 from these reactions have been inconclusive, with many studies failing to detect NO3. In the present work, the reactions of formaldehyde oxide (CH2OO) and acetaldehyde oxide (CH3CHOO) with NO2 are revisited to further explore the product formation over a pressure range of 4-40 Torr. NO3 is not observed; however, temporally resolved and [NO2]-dependent signal is observed at the mass of the Criegee-NO2 adduct for both formaldehyde-and acetaldehyde-oxide systems, and the structure of this adduct is explored through ab initio calculations. The atmospheric implications of the title reaction are investigated through global modelling.
引用
收藏
页码:313 / 330
页数:18
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