A detailed theoretical study on the reaction mechanisms for the formations of H₂O₂ + ³O₂ from the self‐reaction of HO₂ radicals under the effect of NH₃, H₃N···H₂O, and H₂SO₄ catalysts was performed using the CCSD(T)/CBS//M06‐2X/aug‐cc‐pVTZ method. The rate constant was computed using canonical variational transition state theory (CVT) with small curvature tunneling (SCT). Our results indicate that NH₃‐, H₃N···H₂O‐, and H₂SO₄‐catalyzed reactions could proceed through both one‐step and stepwise routes. Calculated rate constants show that the catalyzed routes in the presence of the three catalysts all prefer stepwise pathways. Compared to the catalytic efficiency of H₂O, the efficiencies of NH₃, H₃N···H₂O, and H₂SO₄ are much lower due to their smaller relative concentrations. The present results have provided a definitive example of how basic and acidic catalysts influence the atmospheric reaction of HO₂ + HO₂ → H₂O₂ + ³O₂. These results further encourage one to consider the effects of basic and acidic catalysts on the related atmospheric reactions. Thus, the present investigation should have broad implications in the gas‐phase reactions of the atmosphere.

中文翻译：

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氨，氨水和硫酸对对流层HO2 + HO2→H2O2 + 3O2反应的影响：逐步机理与一步机理之间的竞争

在NH ₃，H ₃ N···H ₂ O和H ₂ SO的作用下由HO ₂自由基的自反应形成H ₂ O ₂  +  ³ O ₂的反应机理的详细理论研究使用CCSD（T）/ CBS // M06-2X / aug-cc-pVTZ方法执行了_4种催化剂。使用具有小曲率隧穿（SCT）的规范变分过渡状态理论（CVT）计算速率常数。我们的结果表明，NH ₃ ‐，H ₃ N···H ₂ O‐和H ₂ SO ₄催化反应可以通过一步一步进行。计算出的速率常数表明，在三种催化剂存在下的催化路线均偏向逐步路径。与H ₂ O的催化效率相比，NH ₃，H ₃ N···H ₂ O和H ₂ SO ₄的效率由于相对浓度较小而大大降低。目前的结果为碱性和酸性催化剂如何影响HO ₂  + HO ₂  →H ₂ O ₂  +  ³ O ₂的大气反应提供了一个确定的例子。。这些结果进一步鼓励人们考虑碱性和酸性催化剂对相关的大气反应的影响。因此，本研究应该对大气的气相反应具有广泛的意义。