Zhang Peng, Ma Lu, Zhao Meilian, Sun Yuxi, Chen Wanping, Zhang Yunju
Key Laboratory of Photoinduced Functional Materials, Key Laboratory of Inorganic Materials Preparation and Synthesis, Mianyang Normal University, Mianyang, 621000, People's Republic of China.
College of Medical Technology, Chengdu University of Traditional Chinese Medicine Liutai Avenue, Wenjiang District, Chengdu, People's Republic of China.
Sci Rep. 2023 Aug 10;13(1):13014. doi: 10.1038/s41598-023-28783-x.
The influence of a single water molecule on the BrO + HO hydrogen extraction reaction has been explored by taking advantage of CCSD(T)/aug-cc-pVTZ//B3LYP/6-311 + + G(d,p) method. The reaction in the absence of water have two distinct kinds of H-extraction channels to generate HOBr + O (Δ) and HBr + O, and the channel of generation of HOBr + O (Δ) dominated the BrO + HO reaction. The rate coefficient of the most feasible channel for the BrO + HO reaction in the absence of water is estimated to be 1.44 × 10 cm molecule s at 298.15 K, which is consistent with the experiment. The introduction of water made the reaction more complex, but the products are unchanged. Four distinct channels, beginning with HOHO with BrO, HOHO with BrO, BrOHO with HO, HOBrO with HO are researched. The most feasible channels, stemming from HOHO with BrO, and BrOHO with HO, are much slower than the reaction of BrO + HO without water, respectively. Thus, the existence of water molecule takes a negative catalytic role for BrO + HO reaction.
利用CCSD(T)/aug-cc-pVTZ//B3LYP/6-311++G(d,p)方法研究了单个水分子对BrO + HO氢提取反应的影响。无水情况下的反应有两种不同的氢提取通道生成HOBr + O(Δ)和HBr + O，且生成HOBr + O(Δ)的通道主导了BrO + HO反应。无水情况下BrO + HO反应最可行通道的速率系数在298.15 K时估计为1.44×10 cm³·molecule⁻¹·s⁻¹，这与实验结果一致。水的引入使反应更加复杂，但产物不变。研究了从HOHO与BrO、HOHO与BrO、BrOHO与HO、HOBrO与HO开始的四个不同通道。源于HOHO与BrO以及BrOHO与HO的最可行通道分别比无水时的BrO + HO反应慢得多。因此，水分子的存在对BrO + HO反应起负催化作用。
