The BH&HLYP/6-311++G(d,p) level of theory has been employed to investigate the degradation of 3-methoxy-1-propanol (3M1POL) initiated by HO• radicals. Additionally, the CCSD(T)/6-311++G(d,p) method is used to recalculate the single-point energies for each stationary point. For the reaction of 3M1POL + Cl•, the potential energy surface profile has been constructed at the CCSD(T)/cc-pVTZ//MP2/6-311++G(d,p) + 0.95 × ZPE level of theory. The results reveal that the abstractions at three −CH₂– groups of 3M1POL play an important role in the oxidation mechanisms of 3M1POL with HO• radicals and Cl• atoms, yielding three intermediates: CH₃OCH₂CH₂C•HOH, CH₃OCH₂C•HCH₂OH, and CH₃OC•HCH₂CH₂OH. In the atmosphere, these three intermediates undergo further reaction with O₂/NO to generate 3-methoxypropanal, methyl formate, and glycolaldehyde as the major products, which are in good agreement with the experimental observations. The rate coefficient for the HO• + 3M1POL reaction at room temperature is calculated to be 1.50 × 10^–11 cm³ molecule^–1 s^–1, which is in line with the experimentally reported ones. The rate coefficient for the Cl• + 3M1POL reaction at 298 K is 2.07 × 10^–9 cm³ molecule^–1 s^–1, which is about 8 times larger than the experimentally measured values. According to the rate coefficient values obtained at different temperatures, the temperature-dependent rate coefficient expressions are obtained as k (HO • + 3M1POL) = 6.15 × 10^–24 × T^3.9 × exp(1880.1/T) cm³ molecule^–1 s^–1 and k (Cl• + 3M1POL) = 3.53 × 10^–11 × exp(1217/T) cm³ molecule^–1 s^–1 in the temperature range of 260–400 K, respectively. The atmospheric lifetime, along with the ozone formation potential of 3M1POL and the secondary effects of the 3M1POL oxidation products, is also presented.

中文翻译：

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3-甲氧基-1-丙醇与羟基自由基和氯原子反应在大气中降解

BH&HLYP/6-311++G(d,p) 水平的理论已被用来研究HO• 自由基引发的3-甲氧基-1-丙醇(3M1POL) 的降解。此外，CCSD(T)/6-311++G(d,p)方法用于重新计算每个驻点的单点能量。对于 3M1POL + Cl• 的反应，在 CCSD(T)/cc-pVTZ//MP2/6-311++G(d,p) + 0.95 × ZPE 理论水平上构建了势能表面轮廓。结果表明，3M1POL 的三个 -CH ₂ - 基团的抽象在 3M1POL 与 HO• 自由基和 Cl• 原子的氧化机制中发挥着重要作用，产生三种中间体：CH ₃ OCH ₂ CH ₂ C•HOH、CH ₃ OCH ₂ C·HCH ₂ OH、CH ₃ OC·HCH ₂ CH ₂ OH。在大气中，这三种中间体进一步与O ₂ /NO反应，生成主要产物3-甲氧基丙醛、甲酸甲酯和乙醇醛，这与实验观察结果非常吻合。室温下HO• + 3M1POL 反应的速率系数计算为1.50 × 10 ^–11 cm ³ molecular ^–1 s ^–1，与实验报道的速率系数一致。 298 K 下 Cl• + 3M1POL 反应的速率系数为 2.07 × 10 ^–9 cm ³ molecular ^–1 s ^–1，比实验测量值大约 8 倍。根据不同温度下获得的速率系数值，得到与温度相关的速率系数表达式为k (HO • + 3M1POL) = 6.15 × 10 ^–24 × T ^3.9 × exp(1880.1/ T ) cm ³ molecular ^–1 s在 260–400 K 的温度范围内，^–1和k (Cl• + 3M1POL) = 3.53 × 10 ^–11 × exp(1217/ T ) cm ³分子^–1 s ^–1分别。还介绍了 3M1POL 的大气寿命、臭氧形成潜力以及 3M1POL 氧化产物的二次效应。