We measure the UV absorption spectrum of a Criegee intermediate acetaldehyde oxide, CH3CHOO, using time-resolved broadband cavity-enhanced spectrometry. We separate the spectra of the two possible structural isomers, syn- and anti-CH3CHOO, based on their different reactivity towards H2O and SO2. Despite significant overlap, the spectra of the two conformers are sufficiently separated to allow direct conformer-specific probing of the reactions of CH3CHOO with other important tropospheric species.

Rate coefficients are directly determined for the reactions of the Criegee intermediates (CI) CH2OO and CH3CHOO with the two simplest carboxylic acids, formic acid (HCOOH) and acetic acid (CH3COOH), employing two complementary techniques: multiplexed photoionization mass spectrometry and cavity-enhanced broadband ultraviolet absorption spectroscopy. The measured rate coefficients are in excess of 1×10−10 cm3 s−1, several orders of magnitude larger than those suggested from many previous alkene ozonolysis experiments and assumed in atmospheric modeling studies. These results suggest that the reaction with carboxylic acids is a substantially more important loss process for CIs than is presently assumed. Implementing these rate coefficients in global atmospheric models shows that reactions between CI and organic acids make a substantial contribution to removal of these acids in terrestrial equatorial areas and in other regions where high CI concentrations occur such as high northern latitudes, and implies that sources of acids in these areas are larger than previously recognized.

We present the time-resolved UV absorption spectrum of the B̃ (1A′) ← X̃ (1A′) electronic transition of formaldehyde oxide, CH2OO, produced by the reaction of CH2I radicals with O2. In contrast to its UV photodissociation action spectrum, the absorption spectrum of formaldehyde oxide extends to longer wavelengths and exhibits resolved vibrational structure on its low-energy side. Chemical kinetics measurements of its reactivity establish the identity of the absorbing species as CH2OO. Separate measurements of the initial CH2I radical concentration allow a determination of the absolute absorption cross section of CH2OO, with the value at the peak of the absorption band, 355 nm, of σabs = (3.6 ± 0.9) × 10–17 cm2. The difference between the absorption and action spectra likely arises from excitation to long-lived B̃ (1A′) vibrational states that relax to lower electronic states by fluorescence or nonradiative processes, rather than by photodissociation.

Isoprene has the highest emission into Earth’s atmosphere of any nonmethane hydrocarbon. Atmospheric processing of alkenes, including isoprene, via ozonolysis leads to the formation of zwitterionic reactive intermediates, known as Criegee intermediates (CIs). Direct studies have revealed that reactions involving simple CIs can significantly impact the tropospheric oxidizing capacity, enhance particulate formation, and degrade local air quality. Methyl vinyl ketone oxide (MVK-oxide) is a four-carbon, asymmetric, resonance-stabilized CI, produced with 21 to 23% yield from isoprene ozonolysis, yet its reactivity has not been directly studied. We present direct kinetic measurements of MVK-oxide reactions with key atmospheric species using absorption spectroscopy. Direct UV-Vis absorption spectra from two independent flow cell experiments overlap with the molecular beam UV-Vis-depletion spectra reported recently [M. F. Vansco, B. Marchetti, M. I. Lester, J. Chem. Phys. 149, 44309 (2018)] but suggest different conformer distributions under jet-cooled and thermal conditions. Comparison of the experimental lifetime herein with theory indicates only the syn-conformers are observed; anti-conformers are calculated to be removed much more rapidly via unimolecular decay. We observe experimentally and predict theoretically fast reaction of syn-MVK-oxide with SO2 and formic acid, similar to smaller alkyl-substituted CIs, and by contrast, slow removal in the presence of water. We determine products through complementary multiplexed photoionization mass spectrometry, observing SO3 and identifying organic hydroperoxide formation from reaction with SO2 and formic acid, respectively. The tropospheric implications of these reactions are evaluated using a global chemistry and transport model.

The branched C(5) alcohol isopentanol (3-methylbutan-1-ol) has shown promise as a potential biofuel both because of new advanced biochemical routes for its production and because of its combustion characteristics, in particular as a fuel for homogeneous-charge compression ignition (HCCI) or related strategies. In the present work, the fundamental autoignition chemistry of isopentanol is investigated by using the technique of pulsed-photolytic Cl-initiated oxidation and by analyzing the reacting mixture by time-resolved tunable synchrotron photoionization mass spectrometry in low-pressure (8 Torr) experiments in the 550-750 K temperature range. The mass-spectrometric experiments reveal a rich chemistry for the initial steps of isopentanol oxidation and give new insight into the low-temperature oxidation mechanism of medium-chain alcohols. Formation of isopentanal (3-methylbutanal) and unsaturated alcohols (including enols) associated with HO(2) production was observed. Cyclic ether channels are not observed, although such channels dominate OH formation in alkane oxidation. Rather, products are observed that correspond to formation of OH viaβ-C-C bond fission pathways of QOOH species derived from β- and γ-hydroxyisopentylperoxy (RO(2)) radicals. In these pathways, internal hydrogen abstraction in the RO(2)⇄ QOOH isomerization reaction takes place from either the -OH group or the C-H bond in α-position to the -OH group. These pathways should be broadly characteristic for longer-chain alcohol oxidation. Isomer-resolved branching ratios are deduced, showing evolution of the main products from 550 to 750 K, which can be qualitatively explained by the dominance of RO(2) chemistry at lower temperature and hydroxyisopentyl decomposition at higher temperature.

Oxidation of organic compounds in combustion and in Earth's troposphere is mediated by reactive species formed by the addition of molecular oxygen (O2) to organic radicals. Among the most crucial and elusive of these intermediates are hydroperoxyalkyl radicals, often denoted "QOOH." These species and their reactions with O2 are responsible for the radical chain branching that sustains autoignition and are implicated in tropospheric autoxidation that can form low-volatility, highly oxygenated organic aerosol precursors. We report direct observation and kinetics measurements of a QOOH intermediate in the oxidation of 1,3-cycloheptadiene, a molecule that offers insight into both resonance-stabilized and nonstabilized radical intermediates. The results establish that resonance stabilization dramatically changes QOOH reactivity and, hence, that oxidation of unsaturated organics can produce exceptionally long-lived QOOH intermediates.

The rapid reaction of the smallest Criegee intermediate, CHOO, with water dimers is the dominant removal mechanism for CHOO in the Earth's atmosphere, but its products are not well understood. This reaction was recently suggested as a significant source of the most abundant tropospheric organic acid, formic acid (HCOOH), which is consistently underpredicted by atmospheric models. However, using time-resolved measurements of reaction kinetics by UV absorption and product analysis by photoionization mass spectrometry, we show that the primary products of this reaction are formaldehyde and hydroxymethyl hydroperoxide (HMHP), with direct HCOOH yields of less than 10%. Incorporating our results into a global chemistry-transport model further reduces HCOOH levels by 10-90%, relative to previous modeling assumptions, which indicates that the reaction CHOO + water dimer by itself cannot resolve the discrepancy between the measured and predicted HCOOH levels.

We observe chlorine radical dynamics in solution following two-photon photolysis of the solvent, dichloromethane. In neat CH(2)Cl(2), one-third of the chlorine radicals undergo diffusive geminate recombination, and the rest abstract a hydrogen atom from the solvent with a bimolecular rate constant of (1.35 +/- 0.06) x 10(7) M(-1) s(-1). Upon addition of hydrogen-containing solutes, the chlorine atom decay becomes faster, reflecting the presence of a new reaction pathway. We study 16 different solutes that include alkanes (pentane, hexane, heptane, and their cyclic analogues), alcohols (methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol), and chlorinated alkanes (cyclohexyl chloride, 1-chlorobutane, 2-chlorobutane, 1,2-dichlorobutane, and 1,4-dichlorobutane). Chlorine reactions with alkanes have diffusion-limited rate constants that do not depend on the molecular structure, indicating the absence of a potential barrier. Hydrogen abstraction from alcohols is slower than from alkanes and depends weakly on molecular structure, consistent with a small reaction barrier. Reactions with chlorinated alkanes are the slowest, and their rate constants depend strongly on the number and position of the chlorine substituents, signaling the importance of activation barriers to these reactions. The relative rate constants for the activation-controlled reactions agree very well with the predictions of the gas-phase structure-activity relationships.