2NCO + 2N2H反应的理论研究

Xiang Tiancheng, Zhao Yanru, Xu Jingli, Hu Chaopeng
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引用次数: 3

摘要

在B3LYP/6-311G (d,p)水平上研究了2NCO + 2N2H反应的单线态和三重态电位表面。单点能量计算在高级CCSD (T)/6-311G (d,p)下进行,以获得更准确的能量值。DFT计算表明,反应机制主要是2NCO与2N2H的无阻碍加成,在单线态电位表面产生中间的1im3 (OCN-N2H)。加合物1im3从N2H转变为NCO,形成HNCO和N2的产物。由于初始缔合势垒较高,在三重态电位表面上的反应较为困难。
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A theoretical study of the 2NCO + 2N2H reaction

The singlet and triplet potential surfaces of the 2NCO + 2N2H reaction have been investigated at the B3LYP/6-311G (d,p) level. The single-point energy calculations are performed at the high-level CCSD (T)/6-311G (d,p) for more accurate energy values. DFT calculations reveal the reaction mechanism to be mainly a barrierless addition of 2NCO to 2N2H leading to an intermediate 1im3 (OCN–N2H) on the singlet potential surface. The adduct 1im3 goes through an H shift from N2H to NCO, forming the product of HNCO and N2. Due to the higher barrier of initial association, the reaction is more difficult on the triplet potential surface.

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