Chemical Kinetic Study of the Reaction of CH2OO with CH3O2.

Criegee intermediates play an important role in the oxidizing capacity of the Earth's troposphere. Although extensive studies have been conducted on Criegee intermediates in the past decade, their kinetics with radical species remain underexplored. We investigated the kinetics of the simplest Criegee intermediate, CH2OO, with the methyl peroxy radical, CH3O2, as a model system to explore the reactivities of Criegee intermediates with peroxy radicals. Using a multipass UV-Vis spectrometer coupled to a pulsed-laser photolysis flow reactor, CH2OO and CH3O2 were generated simultaneously from the photolysis of CH2I2/CH3I/O2/N2 mixtures with CH2OO measured directly near 340 nm. We determined a reaction rate coefficient kCH2OO+CH3O2 = (1.7 ± 0.5) × 10-11 cm3 s-1 at 294 K and 10 Torr, where the influence of iodine adducts is reduced. This rate coefficient is faster than previous theoretical predictions, highlighting the challenges in accurately describing the interaction between zwitterionic and biradical characteristics of Criegee intermediates.

A white cell based broadband transient UV-vis absorption spectroscopy with pulsed laser photolysis reactors for chemical kinetics under variable temperatures and pressures.

UV-vis spectroscopy is widely used for kinetic studies in physical chemistry, as species' absolute cross-sections are usually less sensitive to experimental conditions (i.e., temperature and pressure). Here, we present the design and characterization of a multipass UV-vis absorption spectroscopy white cell coupled to a pulsed-laser photolysis flow reactor. The glass reactor was designed to facilitate studies of gas phase chemical reactions over a range of conditions (239-293 K and 10-550 Torr). Purged windows mitigate contamination from chemical precursors and photolysis products. We report the measured impact of this purging on temperature uniformity and the absorption length and present some supporting flow calculations. The combined optical setup is unique and enables the photolysis laser to be coaligned with a well-defined absorption pathlength probe beam. This alignment leverages the use of one long-pass filter to increase the spectrum flatness and increase the light intensity vs other systems that use two dichroic mirrors. The probe beam is analyzed with a dual exit spectrograph, customized to split the light between an intensified CCD and photomultiplier tube, enabling simultaneous spectrum and single wavelength detection. This multipass system yields a pathlength of ∼450 cm and minimum observable concentrations of ∼3.7 × 1011 molecule cm-3 (assuming cross-sections ∼1.2 × 10-17 cm2). The temperature profile across the reaction region is ±2 K, defined by the worst-case temperature of 239 K, validated by measurements of the N2O4 equilibrium constant. Finally, the system is implemented to study the simplest Criegee intermediate, demonstrating the instrument performance and advantages of simultaneous spectrum and temporal profile measurements.

Bimolecular Reaction of Methyl-Ethyl-Substituted Criegee Intermediate with SO2.

Methyl-ethyl-substituted Criegee intermediate (MECI) is a four-carbon carbonyl oxide that is formed in the ozonolysis of some asymmetric alkenes. MECI is structurally similar to the isoprene-derived methyl vinyl ketone oxide (MVK-oxide) but lacks resonance stabilization, making it a promising candidate to help us unravel the effects of size, structure, and resonance stabilization that influence the reactivity of atmospherically important, highly functionalized Criegee intermediates. We present experimental and theoretical results from the first bimolecular study of MECI in its reaction with SO2, a reaction that shows significant sensitivity to the Criegee intermediate structure. Using multiplexed photoionization mass spectrometry, we obtain a rate coefficient of (1.3 ± 0.3) × 10-10 cm3 s-1 (95% confidence limits, 298 K, 10 Torr) and demonstrate the formation of SO3 under our experimental conditions. Through high-level theory, we explore the effect of Criegee intermediate structure on the minimum energy pathways for their reactions with SO2 and obtain modified Arrhenius fits to our predictions for the reaction of both syn and anti conformers of MECI with SO2 (ksyn = 4.42 × 1011 T-7.80exp(-1401/T) cm3 s-1 and kanti = 1.26 × 1011 T-7.55exp(-1397/T) cm3 s-1). Our experimental and theoretical rate coefficients (which are in reasonable agreement at 298 K) show that the reaction of MECI with SO2 is significantly faster than MVK-oxide + SO2, demonstrating the substantial effect of resonance stabilization on Criegee intermediate reactivity.

Acetonyl Peroxy and Hydroperoxy Self- and Cross-Reactions: Temperature-Dependent Kinetic Parameters, Branching Fractions, and Chaperone Effects.

The temperature-dependent kinetic parameters, branching fractions, and chaperone effects of the self- and cross-reactions between acetonyl peroxy (CH3C(O)CH2O2) and hydro peroxy (HO2) have been studied using pulsed laser photolysis coupled with infrared (IR) wavelength-modulation spectroscopy and ultraviolet absorption (UVA) spectroscopy. Two IR lasers simultaneously monitored HO2 and hydroxyl (OH), while UVA measurements monitored CH3C(O)CH2O2. For the CH3C(O)CH2O2 self-reaction (T = 270-330 K), the rate parameters were determined to be A = (1.5-0.3+0.4) × 10-13 and Ea/R = -996 ± 334 K and the branching fraction to the alkoxy channel, k2b/k2, showed an inverse temperature dependence following the expression, k2b/k2 = (2.27 ± 0.62) - [(6.35 ± 2.06) × 10-3] T(K). For the reaction between CH3C(O)CH2O2 and HO2 (T = 270-330 K), the rate parameters were determined to be A = (3.4-1.5+2.5) × 10-13 and Ea/R = -547 ± 415 K for the hydroperoxide product channel and A = (6.23-4.4+15.3) × 10-17 and Ea/R = -3100 ± 870 K for the OH product channel. The branching fraction for the OH channel, k1b /k1, follows the temperature-dependent expression, k1b/k1 = (3.27 ± 0.51) - [(9.6 ± 1.7) × 10-3] T(K). Determination of these parameters required an extensive reaction kinetics model which included a re-evaluation of the temperature dependence of the HO2 self-reaction chaperone enhancement parameters due to the methanol-hydroperoxy complex. The second-law thermodynamic parameters for KP,M for the formation of the complex were found to be ΔrH250K° = -38.6 ± 3.3 kJ mol-1 and ΔrS250K° = -110.5 ± 13.2 J mol-1 K-1, with the third-law analysis yielding ΔrH250K° = -37.5 ± 0.25 kJ mol-1. The HO2 self-reaction rate coefficient was determined to be k4 = (3.34-0.80+1.04) × 10-13 exp [(507 ± 76)/T]cm3 molecule-1 s-1 with the enhancement term k4,M″ = (2.7-1.7+4.7) × 10-36 exp [(4700 ± 255)/T]cm6 molecule-2 s-1, proportional to [CH3OH], over T = 220-280 K. The equivalent chaperone enhancement parameter for the acetone-hydroperoxy complex was also required and determined to be k4,A″ = (5.0 × 10-38 - 1.4 × 10-41) exp[(7396 ± 1172)/T] cm6 molecule-2 s-1, proportional to [CH3C(O)CH3], over T = 270-296 K. From these parameters, the rate coefficients for the reactions between HO2 and the respective complexes over the given temperature ranges can be estimated: for HO2·CH3OH, k12 = [(1.72 ± 0.050) × 10-11] exp [(314 ± 7.2)/T] cm3 molecule-1 s-1 and for HO2·CH3C(O)CH3, k15 = [(7.9 ± 0.72) × 10-17] exp [(3881 ± 25)/T] cm3 molecule-1 s-1. Lastly, an estimate of the rate coefficient for the HO2·CH3OH self-reaction was also determined to be k13 = (1.3 ± 0.45) × 10-10 cm3 molecule-1 s-1.

A-Band Absorption Spectrum of the ClSO Radical: Electronic Structure of the Sulfinyl Group.

Sulfur oxide species (RSOx) play a critical role in many fields, ranging from biology to atmospheric chemistry. Chlorine-containing sulfur oxides may play a key role in sulfate aerosol formation in Venus' cloud layer by catalyzing the oxidation of SO to SO2 via sulfinyl radicals (RSO). We present results from the gas-phase UV-vis transient absorption spectroscopy study of the simplest sulfinyl radical, ClSO, generated from the pulsed-laser photolysis of thionyl chloride at 248 nm (at 40 Torr of N2 and 292 K). A weak absorption spectrum from 350 to 480 nm with a peak at 385 nm was observed, with partially resolved vibronic bands (spacing = 226 cm-1), and a peak cross section σ(385 nm) = (7.6 ± 1.9) × 10-20 cm2. From ab initio calculations at the EOMEE-CCSD/ano-pVQZ level, we assigned this band to 12A' ← X2A″ and 22A' ← X2A″ transitions. The spectrum was modeled as a sum of a bound-to-free transition to the 12A' state and a bound-to-bound transition to the 22A' state with similar oscillator strengths; the prediction agreed well with the observed spectrum. We attributed the vibronic structure to a progression in the bending vibration of the 22A' state. Further calculations at the XDW-CASPT2 level predicted a conical intersection between the excited 12A' and 22A' potential energy surfaces near the Franck-Condon region. The geometry of the minimum-energy conical intersection was similar to that of the ground-state geometry. The lack of structure at shorter wavelengths could be evidence of a short excited-state lifetime arising from strong vibronic coupling. From simplified molecular orbital analysis, we attributed the ClSO spectrum to transitions involving the out-of-plane π/π* orbitals along the S-O bond and the in-plane orbital possessing a σ/σ* character along the S-Cl bond. We hypothesize that these orbitals are common to other sulfinyl radicals, RSO, which would share a combination of a strong and a weak transition in the UV (near 300 nm) and visible (400-600 nm) regions.

OH Roaming and Beyond in the Unimolecular Decay of the Methyl-Ethyl-Substituted Criegee Intermediate: Observations and Predictions.

Alkene ozonolysis generates short-lived Criegee intermediates that are a significant source of hydroxyl (OH) radicals. This study demonstrates that roaming of the separating OH radicals can yield alternate hydroxycarbonyl products, thereby reducing the OH yield. Specifically, hydroxybutanone has been detected as a stable product arising from roaming in the unimolecular decay of the methyl-ethyl-substituted Criegee intermediate (MECI) under thermal flow cell conditions. The dynamical features of this novel multistage dissociation plus a roaming unimolecular decay process have also been examined with ab initio kinetics calculations. Experimentally, hydroxybutanone isomers are distinguished from the isomeric MECI by their higher ionization threshold and distinctive photoionization spectra. Moreover, the exponential rise of the hydroxybutanone kinetic time profile matches that for the unimolecular decay of MECI. A weaker methyl vinyl ketone (MVK) photoionization signal is also attributed to OH roaming. Complementary multireference electronic structure calculations have been utilized to map the unimolecular decay pathways for MECI, starting with 1,4 H atom transfer from a methyl or methylene group to the terminal oxygen, followed by roaming of the separating OH and butanonyl radicals in the long-range region of the potential. Roaming via reorientation and the addition of OH to the vinyl group of butanonyl is shown to yield hydroxybutanone, and subsequent C-O elongation and H-transfer can lead to MVK. A comprehensive theoretical kinetic analysis has been conducted to evaluate rate constants and branching yields (ca. 10-11%) for thermal unimolecular decay of MECI to conventional and roaming products under laboratory and atmospheric conditions, consistent with the estimated experimental yield (ca. 7%).

Conformer-Dependent Chemistry: Experimental Product Branching of the Vinyl Alcohol + OH + O2 Reaction.

The concentration of formic acid in Earth's troposphere is underestimated by detailed chemical models compared to field observations. Phototautomerization of acetaldehyde to its less stable tautomer vinyl alcohol, followed by the OH-initiated oxidation of vinyl alcohol, has been proposed as a missing source of formic acid that improves the agreement between models and field measurements. Theoretical investigations of the OH + vinyl alcohol reaction in excess O2 conclude that OH addition to the α carbon of vinyl alcohol produces formaldehyde + formic acid + OH, whereas OH addition to the ß site leads to glycoaldehyde + HO2. Furthermore, these studies predict that the conformeric structure of vinyl alcohol controls the reaction pathway, with the anti-conformer of vinyl alcohol promoting α OH addition, whereas the syn-conformer promotes ß addition. However, the two theoretical studies reach different conclusions regarding which set of products dominate. We studied this reaction using time-resolved multiplexed photoionization mass spectrometry to quantify the product branching fractions. Our results, supported by a detailed kinetic model, conclude that the glycoaldehyde product channel (arising mostly from syn-vinyl alcohol) dominates over formic acid production with a 3.6:1.0 branching ratio. This result supports the conclusion of Lei et al. that conformer-dependent hydrogen bonding at the transition state for OH-addition controls the reaction outcome. As a result, tropospheric oxidation of vinyl alcohol creates less formic acid than recently thought, increasing again the discrepancy between models and field observations of Earth's formic acid budget.

Yields of HONO2 and HOONO Products from the Reaction of HO2 and NO Using Pulsed Laser Photolysis and Mid-Infrared Cavity-Ringdown Spectroscopy.

The reaction of HO2 with NO is one of the most important steps in radical cycling throughout the stratosphere and troposphere. Previous literature experimental work revealed a small yield of nitric acid (HONO2) directly from HO2 + NO. Atmospheric models previously treated HO2 + NO as radical recycling, but inclusion of this terminating step had large effects on atmospheric oxidative capacity and the concentrations of HONO2 and ozone (O3), among others. Here, the yield of HONO2, φHONO2, from the reaction of HO2 + NO was investigated in a flow tube reactor using mid-IR pulsed-cavity ringdown spectroscopy. HO2, produced by pulsed laser photolysis of Cl2 in the presence of methanol, reacted with NO in a buffer gas mixture of N2 and CO between 300 and 700 Torr at 278 and 300 K. HONO2 and its weakly bound isomer HOONO were directly detected by their v1 absorption bands in the mid-IR region. CO was used to suppress HONO2 produced from OH + NO2 and exploit a chemical amplification scheme, converting OH back to HO2. Under the experimental conditions described here, no evidence for the formation of either HONO2 or HOONO was observed from HO2 + NO. Using a comprehensive chemical model, constrained by observed secondary reaction products, all HONO2 detected in the system could be accounted for by OH + NO2. At 700 ± 14 Torr and 300 ± 3 K, φHONO2 = 0.00 ± 0.11% (2σ) with an upper limit of 0.11%. If all of the observed HONO2 was attributed to the HO2 + NO reaction, φHONO2 = 0.13 ± 0.07% with an upper limit of 0.20%. At 278 ± 2 K and 718 ± 14 Torr, we determine an upper limit, φHONO2 ≤ 0.37%. Our measurements are significantly lower than those previously reported, lying outside of the uncertainty of the current experimental and recommended literature values.

Spectroscopic and Kinetic Studies of the ClSO Radical from Cl2SO Photolysis.

Thionyl chloride (Cl2SO) serves as a common Cl atom source in widespread applications of chlorine chemistry though little is known about the reactivity and spectroscopy of the ClSO radical after a Cl-S bond cleavage. We performed a Pulsed Laser Photolysis experiment to detect ClSO from Cl2SO photolysis at 248 nm in a gas-flow reactor by time-resolved UV-vis transient absorption spectroscopy. A few chemical tests, using I2 and NO2, suggested the structured absorption band between 260 and 320 nm belonged to ClSO radical and that the termolecular ClSO + Cl + M → Cl2SO association reaction occurred. From EOMIP-CCSD/ano-pVQZ calculations, the ClSO band was assigned to the 12A″ ← X2A″ transition involving the π* ← π transition of the SO bond and the vibrational progression to the SO stretching mode of the 12A″ state, with a maximum cross-section = (2.0 ± 0.5) × 10-18 cm2 near 286 nm (1σ uncertainty) and an average spacing of vibrational structure of 658 cm-1. The rapid decay of the ClSO signal monitored near 303 nm could be fit to a second-order kinetic model over 10-90 Torr, which yields an effective bimolecular rate coefficient kCl+ClSO = (1.48 ± 0.42) × 10-11 cm3 molecule-1 s-1 at 292 K and 90 Torr (1σ uncertainty). This fast recombination reaction suggests that Cl-containing SOx species might act as significant Cl atom reservoirs in sulfur oxide-rich environments such as Venus' atmosphere. Moreover, the reported UV spectrum provides a new means for monitoring the ClSO radicals.

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

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.

Pressure and Temperature Dependencies of Rate Coefficients for the Reaction OH + NO2 + M → Products.

The OH + NO2 reaction is a critically important process for radical chain termination in the atmosphere with a major impact on the ozone budgets of the troposphere and stratosphere. Rate constants for the reaction of OH + NO2 + M → products have been measured under conditions relevant to the upper troposphere/lower stratosphere with a laser photolysis-laser-induced fluorescence (LP-LIF) technique augmented by in situ optical spectroscopy for quantification of [NO2]. The experiments are carried out over the temperature range of 230-293 K and the pressure range 50-750 Torr of N2 and air and as a function of [O2]. The observed rate coefficients in N2 agree with the newest experimental literature data sets and are within experimental uncertainty of current recommended literature values at 293 K but are systematically higher by up to 22% at 700 Torr and 230 K. The efficacy of different falloff parametrizations has been examined and compared to those in literature sources. The collisional quenching efficiency of O2 was found to be in excellent agreement with current literature sources, and rate coefficients determined in air at 293 and 245 K were observed to be within uncertainty of the rate coefficients measured in N2 bath gas. This work has improved confidence in the literature rate coefficients under conditions of the lower troposphere (∼760 Torr, 280-310 K) toward the stratosphere (10-100 Torr, 220-250 K).

Formic acid catalyzed isomerization and adduct formation of an isoprene-derived Criegee intermediate: experiment and theory.

Isoprene is the most abundant non-methane hydrocarbon emitted into the Earth's atmosphere. Ozonolysis is an important atmospheric sink for isoprene, which generates reactive carbonyl oxide species (R1R2C[double bond, length as m-dash]O+O-) known as Criegee intermediates. This study focuses on characterizing the catalyzed isomerization and adduct formation pathways for the reaction between formic acid and methyl vinyl ketone oxide (MVK-oxide), a four-carbon unsaturated Criegee intermediate generated from isoprene ozonolysis. syn-MVK-oxide undergoes intramolecular 1,4 H-atom transfer to form a substituted vinyl hydroperoxide intermediate, 2-hydroperoxybuta-1,3-diene (HPBD), which subsequently decomposes to hydroxyl and vinoxylic radical products. Here, we report direct observation of HPBD generated by formic acid catalyzed isomerization of MVK-oxide under thermal conditions (298 K, 10 torr) using multiplexed photoionization mass spectrometry. The acid catalyzed isomerization of MVK-oxide proceeds by a double hydrogen-bonded interaction followed by a concerted H-atom transfer via submerged barriers to produce HPBD and regenerate formic acid. The analogous isomerization pathway catalyzed with deuterated formic acid (D2-formic acid) enables migration of a D atom to yield partially deuterated HPBD (DPBD), which is identified by its distinct mass (m/z 87) and photoionization threshold. In addition, bimolecular reaction of MVK-oxide with D2-formic acid forms a functionalized hydroperoxide adduct, which is the dominant product channel, and is compared to a previous bimolecular reaction study with normal formic acid. Complementary high-level theoretical calculations are performed to further investigate the reaction pathways and kinetics.

Acetonyl Peroxy and Hydro Peroxy Self- and Cross-Reactions: Kinetics, Mechanism, and Chaperone Enhancement from the Perspective of the Hydroxyl Radical Product.

Pulsed laser photolysis coupled with infrared (IR) wavelength modulation spectroscopy and ultraviolet (UV) absorption spectroscopy was used to study the kinetics and branching fractions for the acetonyl peroxy (CH3C(O)CH2O2) self-reaction and its reaction with hydro peroxy (HO2) at a temperature of 298 K and pressure of 100 Torr. Near-IR and mid-IR lasers simultaneously monitored HO2 and hydroxyl, OH, respectively, while UV absorption measurements monitored the CH3C(O)CH2O2 concentrations. The overall rate constant for the reaction between CH3C(O)CH2O2 and HO2 was found to be (5.5 ± 0.5) × 10-12 cm3 molecule-1 s-1, and the branching fraction for OH yield from this reaction was directly measured as 0.30 ± 0.04. The CH3C(O)CH2O2 self-reaction rate constant was measured to be (4.8 ± 0.8) × 10-12 cm3 molecule-1 s-1, and the branching fraction for alkoxy formation was inferred from secondary chemistry as 0.33 ± 0.13. An increase in the rate of the HO2 self-reaction was also observed as a function of acetone (CH3C(O)CH3) concentration which is interpreted as a chaperone effect, resulting from hydrogen-bond complexation between HO2 and CH3C(O)CH3. The chaperone enhancement coefficient for CH3C(O)CH3 was determined to be kA″ = (4.0 ± 0.2) × 10-29 cm6 molecule-2 s-1, and the equilibrium constant for HO2·CH3C(O)CH3 complex formation was found to be Kc(R14) = (2.0 ± 0.89) × 10-18 cm3 molecule-1; from these values, the rate constant for the HO2 + HO2·CH3C(O)CH3 reaction was estimated to be (2 ± 1) × 10-11 cm3 molecule-1 s-1. Results from UV absorption cross-section measurements of CH3C(O)CH2O2 and prompt OH radical yields arising from possible oxidation of the CH3C(O)CH3-derived alkyl radical are also discussed. Using theoretical methods, no likely pathways for the observed prompt OH radical formation have been found and the prompt OH radical yields thus remain unexplained.

Direct kinetic measurements and theoretical predictions of an isoprene-derived Criegee intermediate.

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.

Experimental Evidence of Dioxole Unimolecular Decay Pathway for Isoprene-Derived Criegee Intermediates.

Ozonolysis of isoprene, one of the most abundant volatile organic compounds emitted into the Earth's atmosphere, generates two four-carbon unsaturated Criegee intermediates, methyl vinyl ketone oxide (MVK-oxide) and methacrolein oxide (MACR-oxide). The extended conjugation between the vinyl substituent and carbonyl oxide groups of these Criegee intermediates facilitates rapid electrocyclic ring closures that form five-membered cyclic peroxides, known as dioxoles. This study reports the first experimental evidence of this novel decay pathway, which is predicted to be the dominant atmospheric sink for specific conformational forms of MVK-oxide (anti) and MACR-oxide (syn) with the vinyl substituent adjacent to the terminal O atom. The resulting dioxoles are predicted to undergo rapid unimolecular decay to oxygenated hydrocarbon radical products, including acetyl, vinoxy, formyl, and 2-methylvinoxy radicals. In the presence of O2, these radicals rapidly react to form peroxy radicals (ROO), which quickly decay via carbon-centered radical intermediates (QOOH) to stable carbonyl products that were identified in this work. The carbonyl products were detected under thermal conditions (298 K, 10 Torr He) using multiplexed photoionization mass spectrometry (MPIMS). The main products (and associated relative abundances) originating from unimolecular decay of anti-MVK-oxide and subsequent reaction with O2 are formaldehyde (88 ± 5%), ketene (9 ± 1%), and glyoxal (3 ± 1%). Those identified from the unimolecular decay of syn-MACR-oxide and subsequent reaction with O2 are acetaldehyde (37 ± 7%), vinyl alcohol (9 ± 1%), methylketene (2 ± 1%), and acrolein (52 ± 5%). In addition to the stable carbonyl products, the secondary peroxy chemistry also generates OH or HO2 radical coproducts.

Reaction kinetics of OH + HNO3 under conditions relevant to the upper troposphere/lower stratosphere.

The OH initiated oxidation of HNO3 in the UT/LS plays an important role in controlling the O3 budget, removing HOx radicals whilst driving NOx/y partitioning chemistry by yielding NO3 radicals: OH + HNO3 → H2O + NO3. In this paper, k1(T, P) was measured using OH (A ← X) Laser Induced Fluorescence (LIF) and the data was modelled over the 223-298 K temperature and 25-750 Torr pressure ranges, using the modified Lindemann-Hinshelwood expression , where k0 = 5.2 × 10-14 exp(200/T) cm3 s-1, k2 = 8.4 × 10-17 exp(1900/T) cm3 s-1 and k3 = 1.6 × 10-34 exp(1745/T) cm3 s-1. A significant source of experimental uncertainty derives from accurate determination of HNO3 concentration, which is impacted by heterogeneous uptake of the low volatility HNO3 onto cold surfaces of the reactors. Our results represent the determination of k1(T, P) using two different in situ [HNO3] measurements: VUV absorption and a new two photon Photolysis Induced Fluoresence (PIF). Experimental results are discussed along with a computational master equation calculation (MESMER), which highlight the need for further theoretical study into the OH + HNO3 mechanism and potential energy surface. The atmospheric impact of these new rate constants were modelled using the STOCHEM-CRI chemistry transport global model, which have shown a small reduction in global budgets of key atmospheric species, with more significant changes in the NOx/HNO3 ratio, peaking in the tropical upper troposphere regions.