Reactions Of Criegee Intermediates Research Articles

Molecular mechanisms and atmospheric implications of the simplest criegee intermediate and hydrochloric acid chemistry in the gas phase and at the aqueous interfaces

The atmospheric chemistry of Criegee Intermediates has become a frontier research point in environmental pollution in recent years. In this work, quantum chemical calculations and Born-Oppenheimer Molecular Dynamics (BOMD) simulations were employed to explore the gas phase and aqueous interface behavior of the simplest Criegee Intermediate (sCI, CH2OO) and hydrochloric acid (HCl) reaction. Quantum chemical calculations have revealed that the product of ClCH2OOH (CMHP) formation from the CH2OO + HCl reaction without and with water molecule undergoes a barrierless or near barrierless process in the gas phase. The results of the rate coefficients calculated by the master equation indicate that the gas-phase CMHP formation from the reaction of CH2OO + HCl could compete with the hydrolysis of CH2OO with (H2O)2 at the altitude of 15 km. BOMD simulations at the aqueous interfaces show that the CH2OO + HCl reaction occurs through stepwise mechanisms that are distinct from those in the gas phase. Three different interfacial reaction channels were identified: i) CMHP direct formation, ii) water-mediated CMHP formation, and iii) HCl-mediated hydroxymethyl hydroperoxide (HMHP) formation, and completed in picosecond time scales. Considering the harsh reaction conditions between CH2OO and HCl at the interface (i.e., the two molecules must be sufficiently close to form the CH2OO-HCl complex), the route of HMHP formation via the hydrolysis of CH2OO remains the main atmospheric loss pathway of CH2OO at the aqueous interfaces. Interestingly, molecular dynamic simulations in nanosecond time scales reveal that the formed CMHP in the gas phase has a tendency to aggregate with sulfuric acids, ammonia, and water molecules to form stable clusters within 213–278 K. The present results for the CMHP and HMHP formations from the sCI-HCl chemistry in the atmosphere will enhance our comprehension of the atmospheric behavior of Criegee intermediates in urban and marine pollution areas.

Hydrolysis reactivity reveals significant seasonal variation in the composition of organic peroxides in ambient PM2.5

Atmospheric organic peroxides (POs) play a key role in the formation of O3 and secondary organic aerosol (SOA), impacting both air quality and human health. However, there still remain technical challenges in investigating the reactivity of POs in ambient aerosols due to the instability and lack of standards for POs, impeding accurate evaluation of their environmental impacts. In the present study, we conducted the first attempt to categorize and quantify POs in ambient PM2.5 through hydrolysis, which is an important transformation pathway for POs, thus revealing the reactivities of various POs. POs were generally categorized into hydrolyzable POs (HPO) and unhydrolyzable POs (UPO). HPO were further categorized into three groups: short-lifetime HPO (S-HPO), intermediate-lifetime HPO (I-HPO), and long-lifetime HPO (L-HPO). S-HPO and L-HPO are typically formed from Criegee intermediate (CI) and RO2 radical reactions, respectively. Results show that L-HPO are the most abundant HPO, indicating the dominant role of RO2 pathway in HPO formation. Despite their lower concentration compared to L-HPO, S-HPO make a major contribution to the HPO hydrolysis rate due to their faster rate constants. The hydrolysis of PM2.5 POs accounts for 19 % of the nighttime gas-phase H2O2 growth during the summer observation, constituting a noteworthy source of gas-phase H2O2 and contributing to the atmospheric oxidation capacity. Seasonal and weather conditions significantly impact the composition of POs, with HPO concentrations in summer being significantly higher than those in winter and elevated under rainy and nighttime conditions. POs are mainly composed of HPO in summer, while in winter, POs are dominated by UPO.

Observational evidence for Criegee intermediate oligomerization reactions relevant to aerosol formation in the troposphere

Observational evidence for Criegee intermediate oligomerization reactions relevant to aerosol formation in the troposphere

Temperature-Dependent Kinetics of the Reactions of the Criegee Intermediate CH2OO with Hydroxyketones.

Though there is a growing body of literature on the kinetics of CIs with simple carbonyls, CI reactions with functionalized carbonyls such as hydroxyketones remain unexplored. In this work, the temperature-dependent kinetics of the reactions of CH2OO with two hydroxyketones, hydroxyacetone (AcOH) and 4-hydroxy-2-butanone (4H2B), have been studied using a laser flash photolysis transient absorption spectroscopy technique and complementary quantum chemistry calculations. Bimolecular rate constants were determined from CH2OO loss rates observed under pseudo-first-order conditions across the temperature range 275-335 K. Arrhenius plots were linear and yielded T-dependent bimolecular rate constants: kAcOH(T) = (4.3 ± 1.7) × 10-15 exp[(1630 ± 120)/T] and k4H2B(T) = (3.5 ± 2.6) × 10-15 exp[(1700 ± 200)/T]. Both reactions show negative temperature dependences and overall very similar rate constants. Stationary points on the reaction energy surfaces were characterized using the composite CBS-QB3 method. Transition states were identified for both 1,3-dipolar cycloaddition reactions across the carbonyl and 1,2-insertion/addition at the hydroxyl group. The free-energy barriers for the latter reaction pathways are higher by ∼4-5 kcal mol-1, and their contributions are presumed to be negligible for both AcOH and 4H2B. The cycloaddition reactions are highly exothermic and form cyclic secondary ozonides that are the typical primary products of Criegee intermediate reactions with carbonyl compounds. The reactivity of the hydroxyketones toward CH2OO appears to be similar to that of acetaldehyde, which can be rationalized by consideration of the energies of the frontier molecular orbitals involved in the cycloaddition. The CH2OO + hydroxyketone reactions are likely too slow to be of significance in the atmosphere, except at very low temperatures.

Rapid Atmospheric Reactions between Criegee Intermediates and Hypochlorous Acid.

Hypochlorous acid (HOCl) is a paramount compound in the atmosphere due to its significant contribution to both tropospheric oxidation capacity and ozone depletion. The main removal routes for HOCl are photolysis and the reaction with OH during the daytime, while these processes are unimportant during the nighttime. Here, we report the rapid reactions of Criegee intermediates (CH2OO and anti/syn-CH3CHOO) with HOCl by using high-level quantum chemical methods as the benchmark; their accuracy is close to coupled cluster theory with single, double, and triple excitations and quasiperturbative connected quadruple excitations with a complete basis limit by extrapolation [CCSDT(Q)/CBS]. Their rate constants have been calculated by using a dual-level strategy; this combines conventional transition state theory calculated at the benchmark level with variational transition state theory with small-curvature tunneling by a validated density functional method. We find that the introduction of the methyl group into Criegee intermediates not only affects their reactivities but also exerts a remarkable influence on anharmonicity. The calculated results uncover that anharmonicity increases the rate constants of CH2OO + HOCl by a factor of 18-5, while it is of minor importance in the anti/syn-CH3CHOO + HOCl reaction at 190-350 K. The present findings reveal that the loose transition state for anti-CH3CHOO and HOCl is a rate-determining step at 190-350 K. We also find that the reaction of Criegee intermediates with HOCl contributes significantly to the sink of HOCl during the nighttime in the atmosphere.

New insights into the mechanism and kinetics of the addition reaction of unsaturated Criegee intermediates to CF3COOH and tropospheric implications.

In this work, we have investigated the mechanism, thermochemistry and kinetics of the reaction of syn-cis-CH2RzCRyCO+O- (where Rz, Ry = H, CH3-) unsaturated Criegee intermediates (CIs) with CF3COOH using quantum chemical methods. The rate coefficients for the barrierless reactions were calculated using variable reaction coordinate variational transition state theory (VRC-VTST). For the syn-cis-CH2RzCRyCO+O- conformation in which conjugated CC and CO double bonds are aligned with each other, we propose a new pathway for the unidirectional addition of an OC-OH molecule (CF3COOH) to the CC double bond of syn-cis-CH2RzCRyCO+O-. The rate coefficient for the 1,4-CC addition reaction at 298 K is ∼10-10 to 10-11 cm3 s-1, resulting in the formation of CF3C(O)OCH2CRzRyCOOH trifluoroacetate alkyl allyl hydroperoxide (TFAAAH) as a new transitory adduct. It can act as a precursor for the formation of secondary organic aerosols (SOAs). This novel TFAAAH hydroperoxide was identified through a detailed quantum chemical study of the 1,4-addition mechanism and will provide new insights into the significance of the 1,4-addition reaction of unsaturated Cls with trace tropospheric gases on -CRzCH2 vinyl carbon atoms.

Experimental and theoretical study of Criegee intermediate (CH2OO) reactions with n-butyraldehyde and isobutyraldehyde: kinetics, implications and atmospheric fate.

The reactions of the simplest Criegee intermediate (CH2OO) with n-butyraldehyde (nBD) and isobutyraldehyde (iBD) were studied at 253-318 K and (50 ± 2) torr, using Cavity Ring-down spectroscopy (CRDS). The rate coefficients obtained at room temperature were (2.63 ± 0.14) × 10-12 and (2.20 ± 0.21) × 10-12 cm3 molecule-1 s-1 for nBD and iBD, respectively. Both the reactions show negative temperature-dependency, following equations, knBD(T = 253-318 K) = (11.51 ± 4.33) × 10-14 × exp{(918.1 ± 107.2)/T} and kiBD(T = 253-318 K) = (6.23 ± 2.29) × 10-14 × exp{(1051.4 ± 105.2)/T} cm3 molecule-1 s-1. High-pressure limit rate coefficients were determined from theoretical calculations at the CCSD(T)-F12/cc-pVTZ-F12//B3LYP/6-311+G(2df, 2p) level of theory, with <40% deviation from the experimental results at room temperature and above. The kinetic simulations were performed using a master equation solver to predict the temperature-dependency of the rate coefficients at the experimental pressure, as well as to predict the contribution of individual pathways. The major products predicted from the theoretical calculations were formaldehyde and formic acid, along with butyric acid from nBD and isobutyric acid from iBD reactions.

Barrierless reactions of C2 Criegee intermediates with H2SO4 and their implication to oligomers and new particle formation

The formation of oligomeric hydrogen peroxide triggered by Criegee intermediate maybe contributes significantly to the formation and growth of secondary organic aerosol (SOA). However, to date, the reactivity of C2 Criegee intermediates (CH3CHOO) in areas contaminated with acidic gas remains poorly understood. Herein, high-level quantum chemical calculations and Born-Oppenheimer molecular dynamics (BOMD) simulations are used to explore the reaction of CH3CHOO and H2SO4 both in the gas phase and at the air-water interface. In the gas phase, the addition reaction of CH3CHOO with H2SO4 to generate CH3HC(OOH)OSO3H (HPES) is near-barrierless, regardless of the presence of water molecules. BOMD simulations show that the reaction at the air-water interface is even faster than that in the gas phase. Further calculations reveal that the HPES has a tendency to aggregate with sulfuric acids, ammonias, and water molecules to form stable clusters, meanwhile the oligomerization reaction of CH3CHOO with HPES in the gas phase is both thermochemically and kinetically favored. Also, it is noted that the interfacial HPES− ion can attract H2SO4, NH3, (COOH)2 and HNO3 for particle formation from the gas phase to the water surface. Thus, the results of this work not only elucidate the high atmospheric reactivity of C2 Criegee intermediates in polluted regions, but also deepen our understanding of the formation process of atmospheric SOA induced by Criegee intermediates.

Nontrivial Impact of Relative Humidity on Organic New Particle Formation from Ozonolysis of cis-3-Hexenyl Acetate

The impact of relative humidity (RH) on organic new particle formation (NPF) from the ozonolysis of biogenic volatile organic compounds (BVOCs) remains an area of active debate. Previous reports provide contradictory results, indicating both the depression and enhancement of NPF under conditions of high RH. Herein, we report on the impact of RH on NPF from the dark ozonolysis of cis-3-hexenyl acetate (CHA), a green-leaf volatile (GLV) emitted by vegetation. We show that RH inhibits NPF by this BVOC, essentially shutting it down at RH levels &gt; 1%. While the mechanism for the inhibition of NPF remains unclear, we demonstrate that it is likely not due to increased losses of CHA to the humid chamber walls. New oxidation products dominant under humid conditions are proposed that, based on estimated vapor pressures (VPs), should enhance NPF; however, it is possible that the vapor phase concentration of these low-volatility products is not sufficient to initiate NPF. Furthermore, the reaction of C3-excited state Criegee intermediates (CIs) with water may lead to the formation of small carboxylic acids that do not contribute to NPF. This hypothesis is supported by experiments with quaternary O3 + CHA + α-pinene + RH systems, which showed decreases in total α-pinene-derived NPF at ~0% RH and subsequent recovery at elevated RH.

Atmospheric impact of isoprene-derived Criegee intermediates and isoprene hydroxy hydroperoxide on sulfate aerosol formation in the Asian region

This study revealed the importance of two isoprene-derived pathways in the formation of sulfate aerosol (SO42−(p)), which are related to the gas-phase reactions of Criegee intermediates (CIs) and liquid-phase reactions of isoprene hydroxy hydroperoxide (ISOPOOH), in the atmosphere in the Asian region, using the community multiscale air quality (CMAQ) modeling system. The results showed that the incorporation of both isoprene-derived CIs and ISOPOOH chemistry increased the SO42−(p) concentration in specific domains of Asia, particularly isoprene hotspots, with up to 1% of the total SO42−(p) concentration compared to that obtained by the basic chemical transport model. The impact of ISOPOOH to SO42−(p) formation exhibited a more localized pattern compared to that of CIs, attributed to the tendency of ISOPOOH to condense in low-NO regions. SO42−(p) formation from CIs affected the compositions of nitrate (NO3−), ammonium (NH4+), and secondary organic aerosols (SOA) in the particle phase, and in most of the analyzed sites, those compositions increased from 0.5% to 2.5%. In contrast, SO42−(p) formation from ISOPOOH exhibits a negative impact on SOA, resulting in a potential reduction of up to 5% due to the loss of SOA precursor by incorporating the ISOPOOH uptake reaction. The sensitivity analysis results showed that most of the SO42−(p) was generated by the gas-phase reaction of SO2 with OH; however, the CIs and ISOPOOH also affected the SO42−(p) formation more than the liquid-phase SO42−(p) formations by H2O2, O3, O2, etc.

Reaction of Criegee Intermediates with SO2─A Possible Route for Sulfurous Acid Formation in the Atmosphere

Reaction of Criegee Intermediates with SO₂─A Possible Route for Sulfurous Acid Formation in the Atmosphere

Kinetics of the Simplest Criegee Intermediate Reaction with Water Vapor: Revisit and Isotope Effect.

The kinetics of the simplest Criegee intermediate (CH2OO) reaction with water vapor was revisited. By improving the signal-to-noise ratio and the precision of water concentration, we found that the kinetics of CH2OO involves not only two water molecules but also one and three water molecules. Our experimental results suggest that the decay of CH2OO can be described as d[CH2OO]/dt = -kobs[CH2OO]; kobs = k0 + k1[water] + k2[water]2 + k3[water]3; k1 = (4.22 ± 0.48) × 10-16 cm3 s-1, k2 = (10.66 ± 0.83) × 10-33 cm6 s-1, k3 = (1.48 ± 0.17) × 10-50 cm9 s-1 at 298 K and 300 Torr with the respective Arrhenius activation energies of Ea1 = 1.8 ± 1.1 kcal mol-1, Ea2 = -11.1 ± 2.1 kcal mol-1, Ea3 = -17.4 ± 3.9 kcal mol-1. The contribution of the k3[water]3 term becomes less significant at higher temperatures around 345 K, but it is not ignorable at 298 K and lower temperatures. By quantifying the concentrations of H2O and D2O with a Coriolis-type direct mass flow sensor, the kinetic isotope effect (KIE) was investigated at 298 K and 300 Torr and KIE(k1) = k1(H2O)/k1(D2O) = 1.30 ± 0.32; similarly, KIE(k2) = 2.25 ± 0.44 and KIE(k3) = 0.99 ± 0.13. These mild KIE values are consistent with theoretical calculations based on the variational transition state theory, confirming that the title reaction has a broad and low barrier, and the reaction coordinate involves not only the motion of a hydrogen atom but also that of an oxygen atom. Comparing the results recorded under 300 Torr (N2 buffer gas) with those under 600 Torr, a weak pressure effect of k3 was found. From quantum chemistry calculations, we found that the CH2OO + 3H2O reaction is dominated by the reaction pathways involving a ring structure consisting of two water molecules, which facilitate the hydrogen atom transfer, while the third water molecule is hydrogen-bonded outside the ring. Furthermore, analysis based on dipole capture rates showed that the CH2OO(H2O) + (H2O)2 and CH2OO(H2O)2 + H2O pathways will dominate in the three water reaction.

Substituent Dependence on the Reactions of Criegee Intermediates with Carbon Dioxide and Carbon Monoxide.

Criegee intermediates (CIs), R1 R2 COO, are active molecules produced in the atmosphere from the ozonolysis of alkenes. Here, we systematically evaluated the reactivity of ten CIs with carbon monoxide and carbon dioxide using CCSD(T)-F12/cc-pVTZ-F12//B3LYP/6-311+G(2d,2p) energies and transition state theory. Many previous studies focused on alkyl substitution, but here we evaluated both alkyl and vinyl substitution toward the reactivity by studying five anti-type CIs: CH2 OO, anti-CH3 CHOO, anti-cis-C2 H5 CHOO, anti-trans-MACRO, anti-cis-MACRO; and five syn-type CIs: syn-CH3 CHOO, (CH3 )2 COO, syn-trans-C2 H5 CHOO, syn-trans-MVKO, and syn-cis-MVKO. Our study showed that reactions involving CO2 have a large substituent dependence varying nearly five orders of magnitude, while those involving CO have a much smaller two orders of magnitude difference. Analysis based on the strain interaction model showed that deformation of the CI is an important feature in determining the reactivity with CO2 . On the other hand, we used the OO and CO bond ratios to analyze the zwitterionic character of the CIs. We found that vinyl substitution with π-conjugation results in smaller zwitterionic character and lower reactivity with CO. Lastly, the reactivity of CIs with CO as well as CO2 were found to be not fast enough to be important in an atmospheric context.

Direct gas-phase formation of formic acid through reaction of Criegee intermediates with formaldehyde

Ozonolysis of isoprene is considered to be an important source of formic acid (HCOOH), but its underlying reaction mechanisms related to HCOOH formation are poorly understood. Here, we report the kinetic and product studies of the reaction between the simplest Criegee intermediate (CH2OO) and formaldehyde (HCHO), both of which are the primary products formed in ozonolysis of isoprene. By utilizing time-resolved infrared laser spectrometry with the multifunctional dual-comb spectrometers, the rate coefficient kCH2OO+HCHO is determined to be (4.11 ± 0.25) × 10−12 cm3 molecule−1 s−1 at 296 K and a negative temperature dependence of the rate coefficient is observed and described by an Arrhenius expression with an activation energy of (–1.81 ± 0.04) kcal mol−1. Moreover, the branching ratios of the reaction products HCOOH + HCHO and CO + H2O + HCHO are explored. The yield of HCOOH is obtained to be 37–54% over the pressure (15–60 Torr) and temperature (283–313 K) ranges. The atmospheric implications of the reaction CH2OO + HCHO are also evaluated by incorporating these results into a global chemistry-transport model. In the upper troposphere, the percent loss of CH2OO by HCHO is found by up to 6% which can subsequently increase HCOOH mixing ratios by up to 2% during December-January-February months.

Water Charge Transfer Accelerates Criegee Intermediate Reaction with H2O- Radical Anion at the Aqueous Interface.

Criegee intermediates (CIs) are important carbonyl oxides that may react with atmospheric trace chemicals and impact the global climate. The CI reaction with water has been widely studied and is a main channel for trapping CIs in the troposphere. Previous experimental and computational reports have largely focused on reaction kinetic processes in various CI-water reactions. The molecular-level origin of CI's interfacial reactivity at the water microdroplet surface (e.g., as found in aerosols and clouds) is unclear. In this study, by employing the quantum mechanical/molecular mechanical (QM/MM) Born-Oppenheimer molecular dynamics with the local second-order Møller-Plesset perturbation theory, our computational results reveal a substantial water charge transfer up to ∼20% per water, which creates the surface H2O+/H2O- radical pairs to enhance the CH2OO and anti-CH3CHOO reactivity with water: the resulting strong CI-H2O- electrostatic attraction at the microdroplet surface facilitates the nucleophilic attack to the CI carbonyl by water, which may counteract the apolar hindrance of the substituent to accelerate the CI-water reaction. Our statistical analysis of the molecular dynamics trajectories further resolves a relatively long-lived bound CI(H2O-) intermediate state at the air/water interface, which has not been observed in gaseous CI reactions. This work provides insights into what may alter the oxidizing power of the troposphere by the next larger CIs than simple CH2OO and implicates a new perspective on the role of interfacial water charge transfer in accelerating molecular reactions at aqueous interfaces.

Kinetics of the Simplest Criegee Intermediate CH2OO Reaction with tert-Butylamine

The kinetics of the simplest Criegee intermediate (CH2OO) reaction with tert-butylamine ((CH3)3CNH2) was studied under pseudo-first-order conditions with the OH laser-induced fluorescence (LIF) method at the temperature range of 283-318 K and the pressure range of 5-75 Torr. Our pressure-dependent measurement showed that at 5 Torr─the lowest pressure measured in the current experiment─this reaction was under the high-pressure limit condition. At 298 K, the reaction rate coefficient was measured to be (4.95 ± 0.64) × 10-12 cm3 molecule-1 s-1. The title reaction was observed to be negative temperature-dependent; the activation energy of (-2.82 ± 0.37) kcal mol-1 and the pre-exponential factor of (4.21 ± 0.55) × 10-14 cm3 molecule-1 s-1 were derived from the Arrhenius equation. The rate coefficient of the title reaction is slightly larger than (4.3 ± 0.5) × 10-12 cm3 molecule-1 s-1 of the CH2OO reaction with methylamine; the electron inductive effect and the steric hindrance effect might play a role in contributing to such difference.

The simplest Criegee intermediate CH2OO reaction with dimethylamine and trimethylamine: kinetics and atmospheric implications.

We have used the OH laser-induced fluorescence (LIF) method to measure the kinetics of the simplest Criegee intermediate (CH2OO) reacting with two abundant amines in the atmosphere: dimethylamine ((CH3)2NH) and trimethylamine ((CH3)3N). Our experiments were conducted under pseudo-first-order approximation conditions. The rate coefficients we report are (2.15 ± 0.28) × 10-11 cm3 molecule-1 s-1 for (CH3)2NH at 298 K and 10 Torr, and (1.56 ± 0.23) × 10-12 cm3 molecule-1 s-1 for (CH3)3N at 298 K and 25 Torr with Ar as the bath gas. Both reactions exhibit a negative temperature dependence. The activation energy and pre-exponential factors derived from the Arrhenius equation were (-2.03 ± 0.26) kcal mol-1 and (6.89 ± 0.90) × 10-13 cm3 molecule-1 s-1 for (CH3)2NH, and (-1.60 ± 0.24) kcal mol-1 and (1.06 ± 0.16) × 10-13 cm3 molecule-1 s-1 for (CH3)3N. We propose that the electronegativity of the atom in the co-reactant attached to the C atom of CH2OO, in addition to the dissociation energy of the fragile covalent bonds with H atoms (H-X bond), plays an important role in the 1,2-insertion reactions. Under certain circumstances, the title reactions can contribute to the sink of amines and Criegee intermediates and to the formation of secondary organic aerosol (SOA).

Oligomer formation from the gas-phase reactions of Criegee intermediates with hydroperoxide esters: mechanism and kinetics

Abstract. Hydroperoxide esters, formed in the reactions of carbonyl oxides (also called Criegee intermediates, CIs) with formic acid, play a crucial role in the formation of secondary organic aerosol (SOA) in the atmosphere. However, the transformation mechanism of hydroperoxide esters in the presence of stabilized Criegee intermediates (SCIs) is not well understood. Herein, the oligomerization reaction mechanisms and kinetics of distinct SCI (CH2OO, syn-CH3CHOO, anti-CH3CHOO, and (CH3)2COO) reactions, with their respective hydroperoxide esters and with hydroperoxymethyl formate (HPMF), are investigated in the gas phase using quantum chemical and kinetics modeling methods. The calculations show that the addition reactions of SCIs with hydroperoxide esters proceed through successive insertion of SCIs into hydroperoxide ester to form oligomers that involve SCIs as the repeated chain unit. The saturated vapor pressure and saturated concentration of the formed oligomers decrease monotonically as the number of SCIs is increased. The exothermicity of oligomerization reactions decreases significantly when the number of methyl substituents increases, and the exothermicity of anti-methyl substituted carbonyl oxides is obviously higher than that of syn-methyl substituted carbonyl oxides. The −OOH insertion reaction is energetically more feasible than the −CH insertion pathway in the SCI oligomerization reactions, and the barrier heights increase with increasing the number of SCIs added to the oligomer, except for syn-CH3CHOO. For the reactions of distinct SCIs with HPMF, the barrier of the −OOH insertion pathway shows a dramatic decrease when a methyl substituent occurs at the anti-position, while it reveals a significant increase when a methyl group is introduced at the syn-position and dimethyl substituent. Compared with the rate coefficients of the CH2OO + HPMF reaction, the rate coefficients increase by about 1 order of magnitude when a methyl substituent occurs at the anti-position, whereas the rate coefficients decrease by 1–2 orders of magnitude when a methyl group is introduced at the syn-position. These new findings advance our current understanding of the influence of Criegee chemistry on the formation and growth processes and the chemical compositions of SOA.

Photoionization energetics and dissociation pathways of hydroperoxyethyl formate produced in the reaction of CH3CHOO + formic acid

The bimolecular reaction of Criegee intermediates, zwitterionic carbonyl oxide species produced in alkene ozonolysis, with organic acids leads to formation of functional hydroperoxides implicated in the generation of atmospheric aerosols. This theoretical study using high-level explicitly correlated coupled-cluster theory examines the low energy conformers of hydroperoxyethyl formate [HOOCH(CH3)OCHO, HPEF] formed in the bimolecular reaction of CH3CHOO, a simple alkyl-substituted Criegee intermediate, with formic acid, and the detection of HPEF via photoionization. The vertical and adiabatic ionization energies of HPEF are computed, along with the pathways for dissociative ionization that produce HO2 or OCHO fragments with daughter ions.

Infrared Characterization of the Products and Rate Coefficient of the Reaction between Criegee Intermediate CH2OO and HNO3.

The reactions of Criegee intermediates with HNO3 are important in the polluted urban atmosphere because of their large rate coefficients and the significant concentration of HNO3. Employing a step-scan Fourier-transform spectrometer, we recorded infrared spectra of transient species and end products in the reaction CH2OO + HNO3 upon irradiation of a flowing mixture of CH2I2/HNO3/N2/O2 at 308 nm. Eight bands at 1686, 1426, 1348, 1294, 1052, 965, 891, and 825 cm-1 were assigned to the absorption of the adduct nitrooxymethyl hydroperoxide (NMHP, NO3CH2OOH). Additional products from two dissociation channels were observed. Four bands at 1709, 1325, 1276, and 886 cm-1 were assigned to H2C(O)ONO2 (with coproduct OH), produced from the fission of the O-O bond of internally hot NMHP (NMHP*). Simultaneous detection of H2CO (1746 cm-1), NO2 (1617 cm-1), and HO2 (1392 and 1098 cm-1) indicated a direct cleavage of the N-OC and C-OO bonds of NMHP*. The relative yields of these three channels in pressure range 10-150 Torr were estimated. At 10 Torr, the absorption of internally excited HNO3 near 885 and 1320 cm-1 was also detected at an early stage of the reaction. We investigated also the rate coefficient of the reaction CH2OO + HNO3 by probing the temporal profiles of the formation of NMHP and NO2 under total pressures of 40 and 70 Torr at 298 K. The rate coefficient kHNO3 = (2.4 ± 0.4) × 10-10 cm3 molecule-1 s-1 is less than half the only literature value, (5.4 ± 1.0) × 10-10 cm3 molecule-1 s-1, reported by Foreman et al. (Angew. Chem. Int. Ed. 2016, 55, 10419-10422).