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运用量子化学密度泛函理论UB3LYP/6-311+G*和高级电子相关校正的偶合簇(CCSD(T)/6-311+G*)方法,对CH3CH2,CH3CHCl和CH3CCl2自由基与NO2反应的机理和动力学进行了理论研究,得到了体系的势能面信息和可能的反应机理.根据计算得到的各反应热力学参数及反应能垒,采用传统过渡态理论计算了各反应在温度T=298 K和T=700 K时的速率常数.研究结果表明,该类反应均通过1个中间体和1个过渡态生成产物,产物分别为CH3CHO+HNO,CH3CHO+ClNO和CH3CClO+ClNO.
The reaction of CH3CH2, CH3CHCl and CH3CCl2 free radicals with NO2 was carried out using quantum chemistry density functional theory (UB3LYP / 6-311 + G *) and advanced electronically correlated coupled clusters (CCSD (T) / 6-311 + G * Mechanism and kinetics were studied theoretically and the potential energy surface information and possible reaction mechanism of the system were obtained.According to the calculated thermodynamic parameters and reaction energy barriers of the reaction, the traditional transition state theory was used to calculate the reaction temperature T = 298 K And the rate constant at T = 700 K. The results show that all products of this kind of reaction are formed by one intermediate and one transition state, and the products are CH3CHO + HNO, CH3CHO + ClNO and CH3CClO + ClNO respectively.