High resolution absolute absorption cross sections of the (B)over-tilde1A′-(X)over-tilde1A′ transition of the CH2OO biradical

被引:43
|
作者
Foreman, Elizabeth S. [1 ]
Kapnas, Kara M. [1 ]
Jou, YiTien [1 ]
Kalinowski, Jaroslaw [2 ]
Feng, David [3 ]
Gerber, R. Benny [1 ,2 ,4 ]
Murray, Craig [1 ]
机构
[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA
[2] Univ Helsinki, Dept Chem, FI-00014 Helsinki, Finland
[3] Univ Calif Irvine, Dept Mech & Aerosp Engn, Irvine, CA 92697 USA
[4] Hebrew Univ Jerusalem, Inst Chem, IL-91904 Jerusalem, Israel
基金
以色列科学基金会; 美国国家科学基金会; 芬兰科学院;
关键词
CRIEGEE INTERMEDIATE CH2OO; CONFORMER-DEPENDENT REACTIVITY; I-2/O-3; PHOTOCHEMISTRY; IODINE OXIDES; SPECTRUM; O-2; OZONOLYSIS; SPECTROSCOPY; MECHANISM; RADICALS;
D O I
10.1039/c5cp04977f
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
Carbonyl oxides, or Criegee intermediates, are formed from the gas phase ozonolysis of alkenes and play a pivotal role in night-time and urban area atmospheric chemistry. Significant discrepancies exist among measurements of the strong (B) over tilde (1)A'-(X) over tilde (1)A' electronic transition of the simplest Criegee intermediate, CH2OO in the visible/near-UV. We report room temperature spectra of the (B) over tilde (1)A'-(X) over tilde (1)A' electronic absorption band of CH2OO acquired at higher resolution using both single-pass broadband absorption and cavity ring-down spectroscopy. The new absorption spectra confirm the vibrational structure on the red edge of the band that is absent from ionization depletion measurements. The absolute absorption cross sections over the 362-470 nm range are in good agreement with those reported by Ting et al. Broad-band absorption spectra recorded over the temperature range of 276-357 K were identical within their mutual uncertainties, confirming that the vibrational structure is not due to hot bands.
引用
收藏
页码:32539 / 32546
页数:8
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