Simple Physical Model for the Estimation of Irreversible Dissociation Rates for Bimolecular Complexes.

In this article, we propose a simple method of estimating dissociation rates of bimolecular van der Waals complexes ("wells"), rooted in rigid body dynamics, requiring as input parameters only the bimolecular binding energy, together with the intermolecular equilibrium distance and moments of inertia of the complex. The classical equations of motion are solved for the intermolecular and rotational degrees of freedom in a coordinate system considering only the relative motion of the two molecules, thus bypassing the question of whether the energy of the complex is statistically distributed. Well-escaping trajectories are modeled from these equations, and the escape rate as a function of relative velocity and angular momentum is fitted to an empirical function, which is then integrated over a probability distribution of said quantities. By necessity, this approach makes crude assumptions on the shape of the potential well and neglects the impact of energy quantization, and, more crucially, the coupling between the degrees of freedom included in the equations of motion with those that are not. We quantify the error caused by the first assumption by comparing our model potential with a quantum chemical potential energy surface (PES) and show that while the model does make several compromises and may not be accurate for all classes of bimolecular complexes, it is able to produce physically consistent dissociation rate coefficients within typical atmospheric chemistry confidence intervals for triplet state alkoxyl radical complexes, for which the detailed balance approach has been shown to fail.

Large Gas-Phase Source of Esters and Other Accretion Products in the Atmosphere.

Dimeric accretion products have been observed both in atmospheric aerosol particles and in the gas phase. With their low volatilities, they are key contributors to the formation of new aerosol particles, acting as seeds for more volatile organic vapors to partition onto. Many particle-phase accretion products have been identified as esters. Various gas- and particle-phase formation pathways have been suggested for them, yet evidence remains inconclusive. In contrast, peroxide accretion products have been shown to form via gas-phase peroxy radical (RO2) cross reactions. Here, we show that these reactions can also be a major source of esters and other types of accretion products. We studied α-pinene ozonolysis using state-of-the-art chemical ionization mass spectrometry together with different isotopic labeling approaches and quantum chemical calculations, finding strong evidence for fast radical isomerization before accretion. Specifically, this isomerization seems to happen within the intermediate complex of two alkoxy (RO) radicals, which generally determines the branching of all RO2-RO2 reactions. Accretion products are formed when the radicals in the complex recombine. We found that RO with suitable structures can undergo extremely rapid C-C ß scissions before recombination, often resulting in ester products. We also found evidence of this previously overlooked RO2-RO2 reaction pathway forming alkyl accretion products and speculate that some earlier peroxide identifications may in fact be hemiacetals or ethers. Our findings help answer several outstanding questions on the sources of accretion products in organic aerosol and bridge our knowledge of the gas phase formation and particle phase detection of accretion products. As esters are inherently more stable than peroxides, this also impacts their further reactivity in the aerosol.

An Experimental and Master Equation Investigation of Kinetics of the CH2OO + RCN Reactions (R = H, CH3, C2H5) and Their Atmospheric Relevance.

We have performed direct kinetic measurements of the CH2OO + RCN reactions (R = H, CH3, C2H5) in the temperature range 233-360 K and pressure range 10-250 Torr using time-resolved UV-absorption spectroscopy. We have utilized a new photolytic precursor, chloroiodomethane (CH2ICl), whose photolysis at 193 nm in the presence of O2 produces CH2OO. Observed bimolecular rate coefficients for CH2OO + HCN, CH2OO + CH3CN, and CH2OO + C2H5CN reactions at 296 K are (2.22 ± 0.65) × 10-14 cm3 molecule-1 s-1, (1.02 ± 0.10) × 10-14 cm3 molecule-1 s-1, and (2.55 ± 0.13) × 10-14 cm3 molecule-1 s-1, respectively, suggesting that reaction with CH2OO is a potential atmospheric degradation pathway for nitriles. All the reactions have negligible temperature and pressure dependence in the studied regions. Quantum chemical calculations (ωB97X-D/aug-cc-pVTZ optimization with CCSD(T)-F12a/VDZ-F12 electronic energy correction) of the CH2OO + RCN reactions indicate that the barrierless lowest-energy reaction path leads to a ring closure, resulting in the formation of a 1,2,4-dioxazole compound. Master equation modeling results suggest that following the ring closure, chemical activation in the case of CH2OO + HCN and CH2OO + CH3CN reactions leads to a rapid decomposition of 1,2,4-dioxazole into a CH2O + RNCO pair, or by a rearrangement, into a formyl amide (RC(O)NHC(O)H), followed by decomposition into CO and an imidic acid (RC(NH)OH). The 1,2,4-dioxazole, the CH2O + RNCO pair, and the CO + RC(NH)OH pair are atmospherically significant end products to varying degrees.