Theoretical study on the hydrogen abstraction reactions from hydrazine derivatives by H atom
Theoretical study on the hydrogen abstraction reactions from hydrazine derivatives by H atom
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DOI：
10.1002/kin.21370
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发表时间：
2020-08
影响因子：
1.5
通讯作者：
N. Kanno;Tomohiro Kito
中科院分区：
文献类型：
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作者：
N. Kanno;Tomohiro Kito
采用CBS-QB3//DSD-BLYP-D3(BJ)/Def2-TZVP量子化学计算和过渡态理论计算，结合各种隧道修正方法，从理论上研究了H原子与肼及其甲基衍生物的吸氢反应。通过甲基取代稳定了氨基抽氢反应的产物和过渡态能量。αN位的取代效应是βN位的两倍。另一方面，取代度对甲基脱氢反应的影响可以忽略不计。用正则变分过渡态理论结合小曲率隧道修正计算的N2H4+H反应总速率系数与文献报道值吻合较好，但CH3NHNH2/(CH3)2NNH2+H的计算值略低于实验值。提出了产品比速率系数用于这些燃料燃烧的动力学模拟。
The hydrogen abstraction reactions from hydrazine and its methyl derivatives by the H atom have been investigated theoretically by using CBS‐QB3//DSD‐BLYP‐D3(BJ)/Def2‐TZVP quantum chemical calculations and transition state theory calculations coupled with various tunneling correction methods. Both the products and transition state energies of the hydrogen abstraction from the amino group were stabilized by the methyl group substitution. The substitution effect on theαN site was two times larger than that on theβN site. On the other hand, the substitution effect was negligible on the hydrogen abstraction from the methyl group. The overall rate coefficients of N2H4+ H reaction calculated by canonical variational transition state theory with the small‐curvature tunneling correction agreed well with previously reported values, but those of CH3NHNH2/(CH3)2NNH2+ H were slightly lower than a previous experimental value. The product‐specific rate coefficients have been proposed for the kinetics modeling of these fuels’ combustion.