Direct Dynamics Study on the Hydrogen Abstraction Reaction PH 3 + H → PH 2 + H 2
Direct Dynamics Study on the Hydrogen Abstraction Reaction PH 3 + H → PH 2 + H 2
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PH 3 + H → PH 2 + H 2 夺氢反应的直接动力学研究
DOI：
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发表时间：
1999
期刊：
影响因子：
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通讯作者：
Chia
中科院分区：
文献类型：
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作者：
Xin;Shenmin Li;Jing;Zhenfeng Xu;Zesheng Li;Chia
用从头算直接动力学方法研究了PH 3 + H → PH 2 + H2的夺氢反应。在UQCISD/6-311+G** 水平上计算了反应物、产物和过渡态的几何构型和频率，以及最小能量路径上的12个沿着点，为了得到更可靠的能量，在G2//QCISD水平上进行了单点计算.正、逆反应的势垒分别为3.24和25.99千卡/摩尔。在200 - 1600 K的温度范围内，反应速率常数和活化能通过结合小曲率隧道修正的正则变分过渡态理论计算，并且它们在测量的温度范围内与可用的实验值令人满意地一致。
The hydrogen abstraction reaction PH3 + H → PH2 + H2 has been studied using an ab initio direct dynamic method. The optimized geometries and frequencies were calculated at the UQCISD/6-311+G** level for the reactant, products, and transition state, as well as 12 points along the minimum energy path. In order to obtain more reliable energies, the single-point calculations were carried out at the G2//QCISD level. The potential barriers obtained for the forward and reverse reactions are 3.24 and 25.99 kcal/mol, respectively. Reaction rate constants and activation energies were calculated for the temperature range 200−1600 K by the canonical variational transition state theory incorporating a small-curvature tunneling correction, and they are in satisfactory agreement with the available experimental values over the measured temperature ranges.