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Kinetics and ab initio Studies of Hydrogen Abstraction Reaction "HNCO + HCO →NCO + CH2O"
Zhang Xinzhuang,Xu Zhenfeng,Ji Yongqiang,Feng Wenlin*,Lei Ming
Author NameAffiliationE-mail
Zhang Xinzhuang Faculty of Science, Beijing University of Chemical Technology, Beijing 100029  
Xu Zhenfeng Faculty of Science, Beijing University of Chemical Technology, Beijing 100029  
Ji Yongqiang Faculty of Science, Beijing University of Chemical Technology, Beijing 100029  
Feng Wenlin* Faculty of Science, Beijing University of Chemical Technology, Beijing 100029 gezi319@163.com 
Lei Ming Faculty of Science, Beijing University of Chemical Technology, Beijing 100029  
Abstract:
Using the MP2 method at the 6-311G(d,p) level, the geometries of the reactants, transition state and products of the hydrogen abstraction reaction of isocyanic acid (HNCO) with formyl radical (HCO) have been optimized. Changes of bond lengths of interacting molecules and the stationary point structures were discussed along the minimum energy paths (MEP). It shows that the process of the N-H bond breaking and the C-H bond forming is a concerted reaction. The stationary point energies are corrected by QCISD(T,full) and the potential barrier calculated 91.47 kJ/mol is close to the experimental barrier 108.9 kJ/mol. The rate constants calculated by the CVT method have been carefully compared with the experimental data over the range temperature 500~2500 K.
Key words:  Isocyanic acid, Hydrogen abstraction reaction, ab initio, Formyl radical, Rate constant
FundProject:国家教育部博士点基金资助项目(1999002715).
HNCO+HCO→NCO+CH2O氢转移反应的从头算及动力学研究
张欣庄,徐振峰,冀永强,冯文林*,雷鸣
摘要:
在UMP2(Full)/6-311G(d,p)计算水平上,优化了标题反应的反应物、过渡态、产物的几何结构,沿最小能量途径讨论了异氰酸(HNCO)和甲酰自由基(HCO)发生氢转移反应位能面上驻点的结构以及相互作用分子结构变化.指出该反应是一个N-H键断裂和C-H键生成的协同反应.进一步采用UQCISD(T,Full)方法对反应途径上的驻点进行了单点能量校正,得出该反应的计算位垒是91.47 kJ/mol,与实验值108.92 kJ/mol接近在500~2500K实验温度范围内,运用变分过渡态理论(CVT)计算得到的速率常数与实验观测值进行了比较
关键词:  异氰酸  氢转移反应  ab initio  甲酰基自由基  速率常数
DOI:10.1088/1674-0068/16/2/94-98
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