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本文综述了内禀反应坐标(LEC)方法的基本设想及其基本方程的意义和适用性。并以甲硫醛分子异构化反应和脱氢反应这一典型性的单分子反应过程为侧在4—31G基函数上用量子化学从头计算法做了IRC解析。得到了各反应途经过渡态结构,反应势能曲线,反应活化能和反应热,做出相应的反应路振动分折。由得出的数据计算了各反应的频率因子A值和反应活化熵ΔS~+值以及估算了各反应的速度常数k值,并将结果与甲醛分子单分子过程做了对此。讨论了单分子反应中异构化过程与分解过程竞争中能量因素与结构因素与反应活化性的关系丰富了单分子反应动力学理论。
This paper summarizes the basic idea of intrinsic reaction coordinate (LEC) method and the significance and applicability of its basic equations. And the typical single-molecule reaction process of isomerization and dehydrogenation of methylaldehyde was performed on the 4-31G basis function by ab initio quantum chemical ab initio IRC analysis. The transition state structure, the reaction potential curve, the reaction activation energy and the heat of reaction of each reaction route are obtained, and the corresponding vibration response of the reaction route is made. From the data obtained, the frequency factor A and the entropy ΔS ~ + of each reaction were calculated and the k value of each reaction was estimated, and the result was compared with that of the formaldehyde molecule. The relationship between energy factor and structure factor and reaction activation in the competition of isomerization process and decomposition process in single molecule reaction was discussed. The single molecule reaction kinetics theory was enriched.