【摘要】 用密度泛函理论方法在UB3LYP/ 6 - 311++G(d ,p)并包含零点能水平上计算得到了H2 CO和NO2 反应的势能面 .在势能面上找到了由H2 CO和NO2 反应生成HCO和trans-HONO的两条反应通道 .直接H迁移反应通道的势垒只有 90 5 4kJ·mol-1,是主要的反应通道 ,其TST速率是 7 9cm3·mol-1·s-1,与文献值相符 ;另一条通道是H2 CO异构化为trans-HCOH ,然后C位H迁移 ,最后生成的HOC分子异构化为HCO ,这条通道反应势垒高达348 0 3kJ·mol-1,是一条次要反应通道更多还原

【Abstract】 The potential energy surface for the reaction between H 2CO and NO 2 was investigated by density functional theory at UB3LYP/6-311++G(d,p) level of theory including zero point vibrational energy. Two reaction channels from reactants H 2CO and NO 2 to products HCO and trans -HONO were found on the potential energy surface. The direct hydrogen abstraction reaction from H 2CO by NO 2, which reaction barrier height is 90.54 kJ·mol -1 , is primary reaction channel, and its TST rate is 7.9 cm 3·mol -1 ·s -1 , which is in agreement with experiments. Another reaction channel is firstly isomerization from H 2CO to trans -HCOH that is followed by the C-site hydrogen abstraction reaction, and the next step is from HOC to HCO via a transition state whose reaction barrier is 348.03 kJ·mol -1 . This is a secondary reaction channel.更多还原