论文部分内容阅读
采用QCISD/6-311G犤d,p犦从头算方法,优化了吸氢反应CH2O+O犤3P犦→CHO+OH的反应物、过渡态和产物的几何结构,并用QCISD(t,full)/6-311G//QCISD/6-311G方法对各驻点进行了单点校正,得出正逆反应的活化位垒分别为38.86kJ·mol-1和67.23kJ·mol-1.IRC(内禀反应坐标)分析指出,该反应是一个C-H键断裂和H-O键生成协同进行的反应,而且在反应途径上存在一个引导反应进行的振动模式,其引导反应进行s区间为-0.4～0.75(amu)1/2.在1300～2270K温度范围内运用改进的变分过渡态理论(ICVT),计算了反应速率常数,与实验结果相当一致.
The QCISD / 6-311G 犤 d, p 犦 ab initio method was used to optimize the reactants, transition states and product geometries of the hydrogen-absorbing reaction CH2O + O 犤 3P 犦 → CHO + OH. 6-311G // QCISD / 6-311G method was used to carry out single-point calibration for each stagnation point, and the activation barriers of forward and reverse reaction were 38.86kJ · mol-1 and 67.23kJ · mol-1.IRC (intrinsic reaction The results show that this reaction is a coordinated reaction of CH bond cleavage and HO bond formation, and there is a vibrational mode that leads the reaction in the reaction pathway. The reaction leads to a s interval of -0.4 ~ 0.75 (amu) 1 / 2. Using the improved variational transition state theory (ICVT) in the temperature range of 1300 ~ 2270K, the reaction rate constant was calculated, which is quite consistent with the experimental results.