The mechanism and kinetics of the production of hydroxymethyl hydroperoxide (HMHP) in ethene/ ozone/water gas-phase system were investigated at room temperature (298±2 K) and atmospheric pressure (1×10 5 Pa). The reactants were monitored in situ by long path FTIR spectroscopy. Peroxides were measured by an HPLC post-column fluorescence technique after sampling with a cold trap. The rate constants (k 3 ) of reaction CH 2 O 2 +H 2 O→HMHP (R3) determined by fitting model calculations to experimental data range from (1.6-6.0)×10 −17 cm 3 ·molecule −1 ·s −1 . Moreover, a theoretical study of reaction (R3) was performed using density functional theory at QCISD(T)/6-311+(2d,2p)//B3LYP/6-311+G(2d, 2p) level of theory. Based on the calculation of the reaction potential energy surface and intrinsic reaction coordinates, the classic transitional state theory (TST) derived k 3 (k TST ), canonical variational transition state theory (CVT) derived k 3 (k CVT ), and the corrected k CVT with small-curvature tunneling (k CVT/SCT ) were calculated using Polyrate Version 8.02 program to be 2.47×10 −17 , 2.47×10 −17 and 5.22×10 −17 cm 3 ·molecule −1 ·s −1 , respectively, generally in agreement with those fitted by the model. ethane, ozone, rate constant, HMHP, density functional theoryThe ozonolysis of alkenes is a major pathway for the degradation of alkenes emitted into the atmosphere both anthropogenically and naturally. Ozonolysis is also an important source of atmospheric OH and HO 2 radicals during both day and night [1] . The reaction of ozone with alkenes, such as ethene, is initiated by cycloaddition of ozone across the double bond in ethene, forming a primary ozonide (POZ), according to Criegee [2] . POZ have excess energy due to the high exothermicity of the reaction (ca. 250 kJ/mol), and split rapidly to excited Criegee intermediate CH 2 O 2 ≠ and formaldehyde: CH 2 == CH 2 + O 3 →CH 2 OO ≠ + HCHO (R1) About 60% of CH 2 O 2 ≠ decompose unimoleculary to molecular and radical products: CH 2 OO ≠ →CO 2 + 2H (R2a) CH 2 OO ≠ →CO 2 + H 2 (R2b) CH 2 OO ≠ →CO + H 2 O (R2c) CH 2 OO ≠ →HCO + OH (R2d) The remains of CH 2 O 2 ≠ are collisionally deactivated to form stabilized intermediate CH 2 O 2 [3] : CH 2 OO ≠ + M→CH 2 OO +M (R2e) The lifetime of CH 2 O 2 radicals is sufficiently long to react with numerous atmospheric species [4] , among which H 2 O has received much attention due to its ubiquitous existence on the earth and abundance in the atmosphere. The reaction of CH 2 O 2 with H 2 O was studied initially by Hatakeyama et al. [5] who observed HC 18 OOH and HCO 18 OH but HC 18 O 18 OH in the product of CH 2 O 2 + H 2 18 O reaction, and therefore suggested
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