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Theoretical Study on Mechanism of Reaction of OH with HO2NO2
?Yan Tian,Tian-jing He*,Li He,Fan-chen Liu ,Dong-ming Chen
Author NameAffiliationE-mail
?Yan Tian Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China; School of Science, Anhui Agricultural University, Hefei 230036, China  
Tian-jing He* Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China tj16@ustc.edu.cn 
Li He Department of Electronic Science and Technology, University of Science and Technology of China, Hefei 230026, China  
Fan-chen Liu Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Dong-ming Chen Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Abstract:
The reaction of HO2NO2 (peroxynitric acid, PNA) with OH was studied by the hybrid density functional B3LYP and CBS-QB3 methods. Based on the calculated potential energy surface, five reaction channels, H2O+NO2+O2, HOOH+NO3, NO2+HO3H, HO2+HONO2 and HO2+HOONO, were examined in detail. The major reaction channel is PNA+OH→M1→TS1→H2O+NO2+O2. Taking a pre-equilibrium approximation and using the CBS-QB3 energies, the theoretical rate constant of this channel was calculated as 1.13×10-12 cm3/(molecule s) at 300 K, in agreement with the experimental result. Comparison between reactions of HOONO2+OH and HONO2+OH was carried out. For HOR+OH reactions, the total rate constants increase from R=NO2 to R=ONO2, which is consistent with experimental measurements.
Key words:  Reaction, Peroxynitric acid, ab initio calculation, Rate constant
FundProject:
Theoretical Study on Mechanism of Reaction of OH with HO2NO2
田燕,何天敬*,何力,刘凡镇,陈东明
摘要:
运用密度泛函的B3LYP方法及CBS-QB3方法对HO2NO2(过氧硝酸,PNA)与OH自由基的反应进行了理论研究. 结果表明, 在计算所得的势能面曲线上存在五个产物通道,分别为H2O+NO2+O2、HOOH+NO3、NO2+HO3H、HO2+HONO2和HO2+HOONO. 对这五个通道分别进行了详细的研究,其中最主要的反应通道为:PNA+OH!M1!TS1!H2O+NO2+O2. 采用了一个准平衡近似的方法并运用CBS-QB3基础上的能量计算得到了300K下此反应路径的速率常数值为1.13 £10-1
关键词:  反应,过氧硝酸,从头算,速率常数
DOI:10.1088/1674-0068/21/01/32-38
分类号: