Catalytic effect of (H(2)O) (n) (n = 1-3) clusters on the HO(2) + SO(2) → HOSO + (3)O(2) reaction under tropospheric conditions.
Catalytic effect of (H(2)O) (n) (n = 1-3) clusters on the HO(2) + SO(2) → HOSO + (3)O(2) reaction under tropospheric conditions.
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对流层条件下(H2O)(n) (n=1-3)簇对HO2 SO2 HOSO O-3(2)反应的催化作用
DOI：
10.1039/c9ra00169g
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发表时间：
2019-05-20
期刊：
影响因子：
3.9
通讯作者：
Chen, Long
中科院分区：
文献类型：
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作者：
Wang, Rui;Yao, Qiuyue;Wen, Mingjie;Tian, Shaobo;Wang, Yan;Wang, Zhiyin;Yu, Xiaohu;Shao, Xianzhao;Chen, Long
用CCSD(T)/CBS//M06-2X/AUG-CC-pVTZ方法和小曲率隧道正则变分过渡态理论研究了无催化剂和有(H2O)n(n=1-3)催化剂的HO2+SO2-→HOSO+3O2反应.计算结果表明，与(H_2O)_2和(H_2O)_3相比，H_2O对H_2O_2+SO_2-→-HOSO+_3O_2的氢原子转移催化作用最强。在280.0-320.0 K温度范围内，在0公里高度的大气中，与H_2O的反应占主导地位，与无催化剂的反应相比，有效速率常数大2-3个数量级。此外，值得一提的是，在0公里处，HO2+SO2HoSO+3O2反应与H2O的相关性在很大程度上取决于它与HO2自由基(如HO2+HO2和HO2+NO3反应)和SO2(如→+HO反应)的初级损失机制竞争的能力。计算结果表明，在HO2和→的主要损失机理中，HO2+SO2、HoSO+3O2与H2O的反应是不能忽略的。计算结果还表明，随着海拔高度从0公里增加到15公里，由于水的相对浓度较低，H2O对HOSO和3O2的贡献从99.98%下降到27.27%。随着海拔的升高，HO2+SO2→HOSO+3O2与H2O的反应不能与HO2自由基的初级损失机制相竞争。这些结果为(H2O)n(n=1-3)催化剂提供了新的视角，表明它们不仅影响势垒，而且影响损失机理。目前的发现应该对计算化学和大气化学有广泛的影响。用CCSD(T)/CBS//M06-2X/AUG-CC-pVTZ方法和小曲率隧道正则变分过渡态理论，研究了无(H2O)n和有(H2O)n(n=1-3)的HO2+SO2-→HOSO+3O2反应.
The HO2 + SO2 → HOSO + 3O2 reaction, both without a catalyst and with (H2O)n (n = 1–3) as a catalyst, has been investigated using CCSD(T)/CBS//M06-2X/aug-cc-pVTZ methods, and canonical variational transition state theory with small curvature tunneling (CVT/SCT). The calculated results show that H2O exerts the strongest catalytic role in the hydrogen atom transfer processes of HO2 + SO2 → HOSO + 3O2 as compared with (H2O)2 and (H2O)3. In the atmosphere at 0 km altitude within the temperature range of 280.0–320.0 K, the reaction with H2O is dominant, compared with the reaction without a catalyst, with an effective rate constant 2–3 orders of magnitude larger. In addition, at 0 km, it is worth mentioning that the relevance of the HO2 + SO2 → HOSO + 3O2 reaction with H2O depends heavily on its ability to compete with the primary loss mechanism of HO2 radicals (such as the HO2 + HO2 and HO2 + NO3 reactions) and SO2 (such as the SO2 + HO reaction). The calculated results show that the HO2 + SO2 → HOSO + 3O2 reaction with H2O cannot be neglected in the primary loss mechanism of the HO2 radical and SO2. The calculated results also show that for the formation of HOSO and 3O2, the contribution of H2O decreases from 99.98% to 27.27% with an increase in altitude from 0 km to 15 km, due to the lower relative concentration of water. With the altitude increase, the HO2 + SO2 → HOSO + 3O2 reaction with H2O cannot compete with the primary loss mechanism of HO2 radicals. The present results provide new insight into (H2O)n (n = 1–3) catalysts, showing that they not only affect energy barriers, but also have an influence on loss mechanisms. The present findings should have broad implications in computational chemistry and atmospheric chemistry. The HO2 + SO2 → HOSO + 3O2 reaction without and with (H2O)n (n = 1–3) have been investigated using CCSD(T)/CBS//M06-2X/aug-cc-pVTZ methods, and canonical variational transition state theory with small curvature tunneling.
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影响因子：
2.9
作者：
Anglada, Josep M.;Gonzalez, Javier
通讯作者：
Gonzalez, Javier
影响因子：
3.3
作者：
Fulle, D;Hamann, HF;Hippler, H
通讯作者：
Hippler, H
影响因子：
4.4
作者：
Anderson, JA;Crager, K;Tschumper, GS
通讯作者：
Tschumper, GS
影响因子：
2.9
作者：
Anglada, Josep M.;Hoffman, Gerald J.;Francisco, Joseph S.
通讯作者：
Francisco, Joseph S.
DOI：
10.1098/rspa.1979.0141
发表时间：
1979-01-01
期刊：
PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL PHYSICAL AND ENGINEERING SCIENCES
影响因子：
--
作者：
BURROWS, JP;CLIFF, DI;WILKINSON, JPT
通讯作者：
WILKINSON, JPT