Quantum chemical calculations with the M06-2X method were performed to uncover the ozonolysis mechanism of guaiacol and several hydroxylated, methoxylated, and methylated phenols to improve the understanding of the ozone-induced attenuation of phenolic compounds. The detailed kinetic properties were obtained by the transition state theory (TST) and the Rice−Ramsperger−Kassel−Marcus (RRKM) theory. Results confirm that the primary ozonides originated from guaiacol occupy considerably long retention time than the short-lived primary ozonides formed from vinyl-type compounds in the air. The TST rate constant of guaiacol ozonolysis is calculated with a value of 8.81 × 10^-20 cm³ molecule^-1 s^-1 at room temperature. The RRKM results prove that the rate constant is positively dependent on temperature but shows no relation with pressure. The reactivity of substituted phenols exhibits a strong correlation with the ozone affinity of carbon atoms and the orbital energy difference (E_Lo-Hac) between the lowest unoccupied molecular orbital of O₃ and the highest occupied molecular orbital of phenols. The substituents can reduce the value of E_Lo-Hac and improve the phenols' reactivity, especially when they locate at the ortho- and para-position. The substituents also improve the ozone affinity of carbon atoms due to the electron-withdrawing effect. The methyl group delivers a moderate impact on the reactivity compared to hydroxyl and methoxy groups.

使用M06-2X方法进行了量子化学计算，以揭示愈创木酚和几种羟基化，甲氧基化和甲基化酚的臭氧分解机理，从而增进了对臭氧诱导的酚类化合物衰减的了解。通过过渡态理论（TST）和Rice-Ramsperger-Kassel-Marcus（RRKM）理论获得了详细的动力学特性。结果证实，与空气中由乙烯基类化合物形成的短寿命伯氮氧化物相比，源自愈创木酚的伯氮氧化物占据了相当长的保留时间。愈创木酚臭氧分解的TST速率常数的计算值为8.81×10 ^-20 cm ³分子^-1 s ^-1在室温下。RRKM结果证明速率常数与温度呈正相关，但与压力无关。取代酚的反应性与碳原子的臭氧亲和力和O ₃的最低未占据分子轨道与最高占据的酚分子轨道之间的轨道能量差（E _{L o -H ac}）密切相关。取代基可以降低E _{L o -H ac}的值并改善酚的反应性，尤其是当它们位于邻位和对位时-位置。由于吸电子效应，取代基还改善了碳原子的臭氧亲和力。与羟基和甲氧基相比，甲基对反应活性的影响中等。