Zhang Yongqi, Cheng Yang, Zhang Tianlei, Wang Rui, Ji Jianwei, Xia Yu, Lily Makroni, Wang Zhuqing, Muthiah Balaganesh
Institute of Theoretical and Computational Chemistry, Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, P. R. China.
School of Mechatronics Engineering, Guizhou Minzu University, Guiyang, Guizhou 550025, P. R. China.
Phys Chem Chem Phys. 2022 Aug 3;24(30):18205-18216. doi: 10.1039/d1cp03318b.
Herein, the reaction mechanisms and kinetics for the HO + SO → HOSO + O reaction catalyzed by a water monomer, a water dimer and small clusters of sulfuric acid have been studied theoretically by quantum chemical methods and the Master Equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) rate calculations. The calculated results show that when HO is introduced into the HO + SO reaction, it not only enhances the stability of the reactant complexes by 9.0 kcal mol but also reduces the energy of the transition state by 8.7 kcal mol. As compared with HO, catalysts (HO), HSO, HSO⋯HO and (HSO) are more effective energetically, which not only results from a higher binding energy of 21.3-26.0 kcal mol for the reactant complexes but also from a reduction of the energy of the transition states by 8.6-17.2 kcal mol. Effective rate constant calculations show that, as compared with HO, catalysts (HO), HSO, HSO⋯HO and (HSO) can never become more efficient catalysts within the altitude range of 0-15 km due to their relatively lower concentrations. Besides, at 0 km altitude, the enhancement factor for the HO and ('/) (HO)-assisted HO + SO reaction within the temperature range of 280-320 K was respectively calculated to be 0.31%-0.34% and 0.16%-0.27%, while the corresponding enhancement factor of HO and (HO) at higher altitudes of 5-15 km was respectively found only 0.002%-0.12% and 0.00001%-0.022%, indicating that the contributions of HO and (HO) are not apparent in the gas-phase reaction of HO with SO especially at higher altitude. Overall, the present work will give a new insight into how a water monomer, a water dimer and small clusters of sulfuric acid catalyze the HO + SO → HOSO + O reaction.
在此，通过量子化学方法和主方程/ Rice-Ramsperger-Kassel-Marcus（ME/RRKM）速率计算，从理论上研究了由水单体、水二聚体和硫酸小团簇催化的HO + SO → HOSO + O反应的反应机理和动力学。计算结果表明，当HO引入到HO + SO反应中时，它不仅使反应物络合物的稳定性提高了9.0千卡/摩尔，还使过渡态的能量降低了8.7千卡/摩尔。与HO相比，催化剂（HO）、HSO、HSO⋯HO和（HSO）在能量上更有效，这不仅源于反应物络合物具有21.3 - 26.0千卡/摩尔的更高结合能，还源于过渡态能量降低了8.6 - 17.2千卡/摩尔。有效速率常数计算表明，与HO相比，催化剂（HO）、HSO、HSO⋯HO和（HSO）由于其相对较低的浓度，在0 - 15千米的高度范围内永远不会成为更有效的催化剂。此外，在0千米高度处，在280 - 320 K的温度范围内，HO和（' /）（HO）辅助的HO + SO反应的增强因子分别计算为0.31% - 0.34%和0.16% - 0.27%，而在5 - 15千米的较高高度处，HO和（HO）的相应增强因子分别仅为0.002% - 0.12%和0.00001% - 0.022%，这表明HO和（HO）在HO与SO的气相反应中的贡献不明显，尤其是在较高高度处。总体而言，本工作将为水单体、水二聚体和硫酸小团簇如何催化HO + SO → HOSO + O反应提供新的见解。
