Simplest Criegee Intermediate CH2OO Research Articles

Reaction between Criegee Intermediate CH2OO and Isobutyraldehyde: Kinetics and Atmospheric Implications

AbstractIn the present work, we have investigated the 1,3‐cycloaddition reaction of isobutyraldehyde ((CH3)2CHCHO) with the simplest Criegee intermediate CH2OO using the OH laser‐induced fluorescence (LIF) method in a reaction tube. The experiments were conducted at temperatures and pressures ranging from 280 to 338 K and 5 to 150 Torr. We found that the bimolecular rate coefficient of the reaction is temperature‐ and pressure‐dependent. The measured rate coefficients at 100 Torr are (4.93±0.89), (4.46±0.80), (3.99±0.72), (3.56±0.64), (3.34±0.60), (2.98±0.54), (2.78±0.50)×10−12 cm3 molecule−1 s−1 at 280, 288, 298, 308, 318, 328, and 338 K, respectively. A high‐pressure limit rate coefficient of (4.47±0.80)×10−12 cm3 molecule−1 s−1 was obtained at 298 K by fitting the pressure‐dependent rate coefficients according to the Lindemann mechanism. The Arrhenius plot of the temperature‐dependent rate coefficients results in an activation energy of (−1.86±0.33) kcal mol−1 and a preexponential factor of (1.72±0.31)×10−13 cm3 molecule−1 s−1. In the atmosphere, the reaction of CH2OO with isobutyraldehyde may contribute to the sink of CH2OO in regions where isobutyraldehyde emission is intense under low temperature and low relative humidity conditions.

Computational mechanistic study of the unimolecular dissociation of ethyl hydroperoxide and its bimolecular reactions with atmospheric species

A detailed computational study of the atmospheric reaction of the simplest Criegee intermediate CH2OO with methane has been performed using the density functional theory (DFT) method and high-level calculations. Solvation models were utilized to address the effect of water molecules on prominent reaction steps and their associated energies. The structures of all proposed mechanisms were optimized using B3LYP functional with several basis sets: 6-31G(d), 6-31G (2df,p), 6-311++G(3df,3pd) and at M06-2X/6-31G(d) and APFD/6-31G(d) levels of theory. Furthermore, all structures were optimized at the B3LYP/6-311++G(3df,3pd) level of theory. The intrinsic reaction coordinate (IRC) analysis was performed for characterizing the transition states on the potential energy surfaces. Fifteen different mechanistic pathways were studied for the reaction of Criegee intermediate with methane. Both thermodynamic functions (ΔH and ΔG), and activation parameters (activation energies Ea, enthalpies of activation ΔHǂ, and Gibbs energies of activation ΔGǂ) were calculated for all pathways investigated. The individual mechanisms for pathways A1, A2, B1, and B2, comprise two key steps: (i) the formation of ethyl hydroperoxide (EHP) accompanying with the hydrogen transfer from the alkanes to the terminal oxygen atom of CIs, and (ii) a following unimolecular dissociation of EHP. Pathways from C1 → H1 involve the bimolecular reaction of EHP with different atmospheric species. The photochemical reaction of methane with EHP (pathway E1) was found to be the most plausible reaction mechanism, exhibiting an overall activation energy of 7 kJ mol−1, which was estimated in vacuum at the B3LYP/6-311++G(3df,3pd) level of theory. All of the reactions were found to be strongly exothermic, expect the case of the sulfur dioxide-involved pathway that is predicted to be endothermic. The solvent effect plays an important role in the reaction of EHP with ammonia (pathway F1). Compared with the gas phase reaction, the overall activation energy for the solution phase reaction is decreased by 162 and 140 kJ mol−1 according to calculations done with the SMD and PCM solvation models, respectively.

Fourier-transform microwave spectroscopy on weakly bound complexes of CH2OO with Ar, CO, and N2

Pure rotational transitions of weakly bound complexes of the simplest Criegee intermediate CH2OO with Ar, CO, and N2 are observed by Fourier-transform microwave (FTMW) and FTMW-MW double-resonance spectroscopy. Many of the observed lines show doublet peaks associated with the tunneling splitting between the two equivalent configurations of the complexes. The intermolecular distances of the complexes are derived from the precise rotational constants determined in this study. The separations between two components of the doublet peaks observed for c-type transitions of CH2OO–Ar are satisfactorily demonstrated by a one-dimensional hindered rotor model for the internal rotation of the CH2OO monomer.

Formation of OH radicals from the simplest Criegee intermediate CH2OO and water

Hydroxyl (OH) radicals can convert nitrogen and sulfur oxides to nitric and sulfuric acid, respectively, and oxidize nonmethane hydrocarbons to organic acids, which play an important key role in the environmental chemistry. The famous Criegee intermediates (CIs) are also key species in atmospheric chemistry. The most important loss paths that control CIs levels are suggested to be the reaction with water vapor. To study the reaction mechanism of the simplest CI (CH2OO) with H2O, stationary species and saddle points on the potential energy surface (PES) of CH2OO + H2O have been investigated at CCSD(T)/AUG-cc-pVTZ//B3LYP/6-311++G(2d,2p) level of theory. The computational results indicate that the most feasible channel for the reaction of CH2OO with H2O produces HOCH2O and hydroxyl radicals (OH). Because the highest Gibbs free energy barrier is only 10.5 kcal/mol, this path will be active in atmosphere and OH radical can be produced in this process. Besides, we find a transition state which has not been reported before and explained the mechanism of the formation of a key intermediate. We also scan the formation PES of OH radical from an intermediate and find a loose transition state, which illustrates the mechanism of the producing of OH radical in the reaction of CH2OO with H2O. Here we present a new way of producing OH radicals.

Simultaneous infrared detection of the ICH2OO radical and Criegee intermediate CH2OO: the pressure dependence of the yield of CH2OO in the reaction CH2I + O2.

The simplest Criegee intermediate CH2OO, important in atmospheric reactions, has been recently produced from the reaction of CH2I + O2 and detected with various methods. In this reaction, the yield of CH2OO decreases with increasing pressure because of the stabilization of the adduct ICH2OO, but no definitive spectral identification of ICH2OO has been reported. We recorded the infrared spectrum of ICH2OO using the same reaction under high pressure; the spectrum agrees with that simulated according to theoretical predictions. With direct detection of both CH2OO and ICH2OO, we determined the pressure dependence of the yield of CH2OO. The yield of CH2OO near 1 atm is greater than previously reported values, which might have significant consequences in atmospheric chemistry.

Observation of hydroxymethyl hydroperoxide in a reaction system containing CH2OO and water vapor through pure rotational spectroscopy.

Pure rotational transitions of hydroxymethyl hydroperoxide (HMHP) were observed in the discharged plasma of a CH2I2/O2/water gas mixture, where the water complex with the simplest Criegee intermediate CH2OO has been identified [M. Nakajima and Y. Endo, J. Chem. Phys. 140, 134302 (2014)]. Isotope experiments using heavy water support that the currently observed HMHP molecule was produced by the reaction of CH2OO with water vapor. The observed species was identified as the most stable conformer with the help of quantum chemical calculations. We also clarified that productions of formic acid and dioxirane are promoted by the existence of water vapor in the discharged reaction system.

Infrared identification of the Criegee intermediates syn- and anti-CH₃CHOO, and their distinct conformation-dependent reactivity.

The Criegee intermediates are carbonyl oxides that play critical roles in ozonolysis of alkenes in the atmosphere. So far, the mid-infrared spectrum of only the simplest Criegee intermediate CH2OO has been reported. Methyl substitution of CH2OO produces two conformers of CH3CHOO and consequently complicates the infrared spectrum. Here we report the transient infrared spectrum of syn- and anti-CH3CHOO, produced from CH3CHI + O2 in a flow reactor, using a step-scan Fourier-transform spectrometer. Guided and supported by high-level full-dimensional quantum calculations, rotational contours of the four observed bands are simulated successfully and provide definitive identification of both conformers. Furthermore, anti-CH3CHOO shows a reactivity greater than syn-CH3CHOO towards NO/NO2; at the later period of reaction, the spectrum can be simulated with only syn-CH3CHOO. Without NO/NO2, anti-CH3CHOO also decays much faster than syn-CH3CHOO. The direct infrared detection of syn- and anti-CH3CHOO should prove useful for field measurements and laboratory investigations of the Criegee mechanism.

Spectroscopic characterization of the complex between water and the simplest Criegee intermediate CH2OO

The hydrogen-bonded complex between water and the simplest Criegee intermediate CH2OO was detected by Fourier-transform microwave spectroscopy under a jet-cooled condition. Both a-type and b-type rotational transitions were observed for H2O-CH2OO and D2O-CH2OO. The determined rotational constants enable us to conclude that the complex has an almost planar ring structure with the terminal oxygen atom of CH2OO being a strong proton acceptor.