The comprehensive mechanism and kinetics for CH₂OO with methacrolein (CH₂ = C(CH₃)CHO, MACR) reaction were investigated at the CCSD(T)/6-311+G(2df,2p)//M06-2X/6-311+G(2df,2p) level of theory. The results show that three kinds of mechanisms including cycloaddition, oxidation and insertion have been identified. Among them, the cycloaddition of CH₂OO adding to CO bond of MACR is more favorable, which occurs via a deeply submerged barrier leading to the formation of energized secondary ozonide (SOZ). The nascent SOZ mainly further decomposes into methacrylic acid and formaldehyde or formic acid and methacrolein, in which formic acid generation follows stepwise and concerted mechanism involving a catalysis for rearrangement of CH₂OO by methacrolein. The calculated rate constant for the title reaction at 300 K using canonical variational transition state theory with small curvature tunneling correction is 1.00 × 10⁻¹² cm³ molecule⁻¹ s⁻¹, which is close to the experimental value of (4.4 ± 1.0) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹. The results reveal that the reaction provides a new pathway to produce organic acids. However, the contribution of acids from this reaction is small as its relative lower rate, compared to atmospheric CH₂OO loss occurring through the hydrolysis of CH₂OO + (H₂O)_n (n = 1–2).

在CCSD（T）/ 6-311 + G（2df，2p）// M06-2X /上研究了甲基丙烯醛（CH ₂  = C（CH ₃）CHO，MACR）反应生成CH ₂ OO的综合机理和动力学。6-311 + G（2df，2p）的理论水平。结果表明，已确定了环加成，氧化和插入三种机理。其中，CH ₂ OO与C的环加成反应MACR的O键是更有利的，它是通过深浸的势垒发生的，从而导致形成带电的次级臭氧化物（SOZ）。新生的SOZ主要进一步分解为甲基丙烯酸，甲醛或甲酸和甲基丙烯醛，其中甲酸的产生遵循逐步协调的机制，涉及通过甲基丙烯醛催化CH ₂ OO重排。使用小曲率隧穿校正的规范变分跃迁状态理论计算的标题反应在300 K下的速率常数为1.00×10 ^-12  cm ³ 分子^-1  s ^-1，接近实验值（4.4±1.0） ×10 ^-13  cm ³ 分子^-1  s ^-1。结果表明该反应提供了产生有机酸的新途径。但是，与通过水解CH ₂ OO +（H ₂ O）_n（n = 1-2）引起的大气CH ₂ OO损失相比，该反应中酸的贡献相对较低，因此其贡献较小。