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1. Effect of Carbon Chain Length on Nascent Yields of Stabilized Criegee Intermediates in Ozonolysis of a Series of Terminal Alkenes

   https://doi.org/10.1021/jacs.4c08051  

   Yang, Lei; Zhang, Jingsong (September 2024, Journal of the American Chemical Society)

   The yields of stabilized Criegee intermediates (sCIs), CH2OO and RCHOO (C2H5CHOO, C3H7CHOO, C4H9CHOO, and C5H11CHOO), produced from ozonolysis of asymmetrical 1-alkenes (1-butene, 1-pentene, 1-hexene, and 1-heptene) were investigated at low pressures (5-16 Torr) using cavity ring-down spectroscopy (CRDS) and chemical titration with sulfur dioxide (SO2). By extrapolating the low-pressure measurements to zero-pressure limit, nascent sCI yields were obtained. Combined with our previous studies on ethene and propene ozonolysis, the nascent sCI yields demonstrated an intriguing trend of increasing with the addition of CH2 groups and eventually reached a plateau at around 31% for longer chain 1-alkenes. In particular, the fraction of stabilized CH2OO reached the plateau from 1-butene, indicating that CH2OO was produced with nearly the same internal energy distribution from 1-butene to 1-heptene. The comparison between the experiments and RRKM calculations suggests that the dissociation of primary ozonide (POZ) of O3 + ethene and propene can be treated by statistical theory, while that of O3 + 1-butene to 1-heptene is non-statistical and intramolecular vibrational redistribution (IVR) of the initial energy on the 1,2,3-trioxolane of POZ throughout the entire molecule was incomplete on the dissociation time scale. 

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2. On the formation and the isomer specific detection of methylacetylene (CH ₃ CCH), propene (CH ₃ CHCH ₂ ), cyclopropane (c-C ₃ H ₆ ), vinylacetylene (CH ₂ CHCCH), and 1,3-butadiene (CH ₂ CHCHCH ₂ ) from interstellar methane ice analogues

   https://doi.org/10.1039/C8CP03921F  

   Abplanalp, Matthew J.; Góbi, Sándor; Kaiser, Ralf I. (March 2019, Physical Chemistry Chemical Physics)

   Pure methane (CH 4 ) ices processed by energetic electrons under ultra-high vacuum conditions to simulate secondary electrons formed via galactic cosmic rays (GCRs) penetrating interstellar ice mantles have been shown to produce an array of complex hydrocarbons with the general formulae: C n H 2n+2 ( n = 4–8), C n H 2n ( n = 3–9), C n H 2n−2 ( n = 3–9), C n H 2n−4 ( n = 4–9), and C n H 2n−6 ( n = 6–7). By monitoring the in situ chemical evolution of the ice combined with temperature programmed desorption (TPD) studies and tunable single photon ionization coupled to a reflectron time-of-flight mass spectrometer, specific isomers of C 3 H 4 , C 3 H 6 , C 4 H 4 , and C 4 H 6 were probed. These experiments confirmed the synthesis of methylacetylene (CH 3 CCH), propene (CH 3 CHCH 2 ), cyclopropane (c-C 3 H 6 ), vinylacetylene (CH 2 CHCCH), 1-butyne (HCCC 2 H 5 ), 2-butyne (CH 3 CCCH 3 ), 1,2-butadiene (H 2 CCCH(CH 3 )), and 1,3-butadiene (CH 2 CHCHCH 2 ) with yields of 2.17 ± 0.95 × 10 −4 , 3.7 ± 1.5 × 10 −3 , 1.23 ± 0.77 × 10 −4 , 1.28 ± 0.65 × 10 −4 , 4.01 ± 1.98 × 10 −5 , 1.97 ± 0.98 × 10 −4 , 1.90 ± 0.84 × 10 −5 , and 1.41 ± 0.72 × 10 −4 molecules eV −1 , respectively. Mechanistic studies exploring the formation routes of methylacetylene, propene, and vinylacetylene were also conducted, and revealed the additional formation of the 1,2,3-butatriene isomer. Several of the above isomers, methylacetylene, propene, vinylacetylene, and 1,3-butadiene, have repeatedly been shown to be important precursors in the formation of polycyclic aromatic hydrocarbons (PAHs), but until now their interstellar synthesis has remained elusive. 

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3. Functionalized Hydroperoxide Formation from the Reaction of Methacrolein-Oxide, an Isoprene-Derived Criegee Intermediate, with Formic Acid: Experiment and Theory

   https://doi.org/10.3390/molecules26103058  

   Vansco, Michael F.; Zuraski, Kristen; Winiberg, Frank A.; Au, Kendrew; Trongsiriwat, Nisalak; Walsh, Patrick J.; Osborn, David L.; Percival, Carl J.; Klippenstein, Stephen J.; Taatjes, Craig A.; et al (May 2021, Molecules)

   null (Ed.)

   Methacrolein oxide (MACR-oxide) is a four-carbon, resonance-stabilized Criegee intermediate produced from isoprene ozonolysis, yet its reactivity is not well understood. This study identifies the functionalized hydroperoxide species, 1-hydroperoxy-2-methylallyl formate (HPMAF), generated from the reaction of MACR-oxide with formic acid using multiplexed photoionization mass spectrometry (MPIMS, 298 K = 25 °C, 10 torr = 13.3 hPa). Electronic structure calculations indicate the reaction proceeds via an energetically favorable 1,4-addition mechanism. The formation of HPMAF is observed by the rapid appearance of a fragment ion at m/z 99, consistent with the proposed mechanism and characteristic loss of HO2 upon photoionization of functional hydroperoxides. The identification of HPMAF is confirmed by comparison of the appearance energy of the fragment ion with theoretical predictions of its photoionization threshold. The results are compared to analogous studies on the reaction of formic acid with methyl vinyl ketone oxide (MVK-oxide), the other four-carbon Criegee intermediate in isoprene ozonolysis. 

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4. Emission factors and evolution of SO ₂ measured from biomass burning in wildfires and agricultural fires

   https://doi.org/10.5194/acp-22-15603-2022  

   Rickly, Pamela S.; Guo, Hongyu; Campuzano-Jost, Pedro; Jimenez, Jose L.; Wolfe, Glenn M.; Bennett, Ryan; Bourgeois, Ilann; Crounse, John D.; Dibb, Jack E.; DiGangi, Joshua P.; et al (January 2022, Atmospheric Chemistry and Physics)

   Abstract. Fires emit sufficient sulfur to affect local and regional airquality and climate. This study analyzes SO2 emission factors andvariability in smoke plumes from US wildfires and agricultural fires, as well as theirrelationship to sulfate and hydroxymethanesulfonate (HMS) formation.Observed SO2 emission factors for various fuel types show goodagreement with the latest reviews of biomass burning emission factors,producing an emission factor range of 0.47–1.2 g SO2 kg−1 C.These emission factors vary with geographic location in a way that suggeststhat deposition of coal burning emissions and application ofsulfur-containing fertilizers likely play a role in the larger observedvalues, which are primarily associated with agricultural burning. A 0-D boxmodel generally reproduces the observed trends of SO2 and total sulfate(inorganic + organic) in aging wildfire plumes. In many cases, modeled HMSis consistent with the observed organosulfur concentrations. However, acomparison of observed organosulfur and modeled HMS suggests that multipleorganosulfur compounds are likely responsible for the observations but thatthe chemistry of these compounds yields similar production and loss rates asthat of HMS, resulting in good agreement with the modeled results. Weprovide suggestions for constraining the organosulfur compounds observedduring these flights, and we show that the chemistry of HMS can alloworganosulfur to act as an S(IV) reservoir under conditions of pH > 6 and liquid water content>10−7 g sm−3. This canfacilitate long-range transport of sulfur emissions, resulting in increasedSO2 and eventually sulfate in transported smoke. 

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5. Nonstatistical Unimolecular Decay of the CH ₂ OO Criegee Intermediate in the Tunneling Regime

   https://doi.org/10.1021/acs.jpclett.4c01401  

   Qian, Yujie; Nguyen, Thanh Lam; Franke, Peter R; Stanton, John F; Lester, Marsha I (June 2024, The Journal of Physical Chemistry Letters)

   Unimolecular decay of the formaldehyde oxide (CH2OO) Criegee intermediate proceeds via a 1,3 ring-closure pathway to dioxirane and subsequent rearrangement and/or dissociation to many products including hydroxyl (OH) radicals that are detected. Vibrational activation of jet-cooled CH2OO with two quanta of CH stretch (17-18 kcal mol-1) leads to unimolecular decay at an energy significantly below the transition state barrier of 19.46  0.25 kcal mol-1, refined utilizing a high-level electronic structure method HEAT-345(Q)Λ. The observed unimolecular decay rate of 1.6 +/- 0.4 x 106 s-1 is two orders of magnitude slower than that predicted by statistical unimolecular reaction theory using several different models for quantum mechanical tunneling. The nonstatistical behavior originates from excitation of a CH stretch vibration that is orthogonal to the heavy atom motions along the reaction coordinate and slow intramolecular vibrational energy redistribution due to the sparse density of states. 

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