Ab initio/density functional theory and multichannel RRKM study for the ClO+CH2Oreaction

被引：7

作者：

Tian, Yan ^{[1
]}

Wei, Wen-Mei ^{[1
]}

Tian, Zhi-Mei ^{[1
]}

Yang, Hong-Yi ^{[1
]}

He, Tian-Jing ^{[1
]}

Liu, Fan-Chen ^{[1
]}

Chen, Dong-Ming ^{[1
]}

机构：

[1] Univ Sci & Technol China, Dept Chem Phys, Hefei 230026, Anhui, Peoples R China

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2006年 / 110卷 / 38期

关键词：

D O I：

10.1021/jp061314x

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The potential energy surface for the CH2O + ClO reaction was calculated at the QCISD(T)/6-311G(2d,2p)// B3LYP/6-311G(d, p) level of theory. The rate constants for the lower barrier reaction channels producing HOCl + HCO, H atom, OCH2OCl, cis-HC(O) OCl and trans-HC(O) OCl have been calculated by TST and multichannel RRKM theory. Over the temperature range of 200-2000 K, the overall rate constants were k(200-2000K) = 1.19 x 10(-13)T(0.79) exp(-3000.00/T). At 250 K, the calculated overall rate constant was 5.80 x 10(-17) cm(3) molecule(-1) s(-1), which was in good agreement with the experimental upper limit data. The calculated results demonstrated that the formation of HOCl + HCO was the dominant reaction channel and was exothermic by 9.7 kcal/mol with a barrier of 5.0 kcal/mol. When it retrograded to the reactants CH2O + ClO, an energy barrier of 14.7 kcal/mol is required. Furthermore, when HOCl decomposed into H + ClO, the energy required was 93.3 kcal/mol. These results suggest that the decomposition in both the forward and backward directions for HOCl would be difficult in the ground electronic state.

引用

页码：11145 / 11150

页数：6

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