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Showing papers by "Mitchio Okumura published in 2015"


Journal ArticleDOI
TL;DR: The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical, hydrogen peroxide, and formaldehyde have been measured from their first ionization thresholds to 12.008 eV.
Abstract: The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical (HO2), hydrogen peroxide (H2O2), and formaldehyde (H2CO) have been measured from their first ionization thresholds to 12.008 eV. HO2, H2O2, and H2CO were generated from the oxidation of methanol initiated by pulsed-laser-photolysis of Cl2 in a low-pressure slow flow reactor. Reactants, intermediates, and products were detected by time-resolved multiplexed synchrotron photoionization mass spectrometry. Absolute concentrations were obtained from the time-dependent photoion signals by modeling the kinetics of the methanol oxidation chemistry. Photoionization cross sections were determined at several photon energies relative to the cross section of methanol, which was in turn determined relative to that of propene. These measurements were used to place relative photoionization spectra of HO2, H2O2, and H2CO on an absolute scale, resulting in absolute photoionization spectra.

69 citations


Journal ArticleDOI
13 Feb 2015-Science
TL;DR: It is shown that the simplest CI, formaldehyde oxide (CH2OO), reacts rapidly with the water dimer, (H2O)2, and the impact of CIs on atmospheric composition may be limited if they react rapidly with water.
Abstract: Alkenes constitute a large fraction of the natural and human-made volatile organic compounds (VOCs) that are emitted into the troposphere. Their oxidation products degrade air quality and contribute to climate warming. Alkene oxidation is thought to involve Criegee intermediates (CIs), highly reactive molecules that form when ozone reacts with alkenes. However, the impact of CIs may be limited if they react rapidly with water. Modelers have found it difficult to quantify the effect of CIs on atmospheric composition, because laboratory data on CI reactions with water have been contradictory. On page 751 of this issue, Chao et al. (1) show that the simplest CI, formaldehyde oxide (CH_2OO), reacts rapidly with the water dimer, (H_2O)_2. Similar results are reported by Lewis et al. (2).

9 citations