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用量化从头算方法在MP4(SDTQ)理论水平上首次考察了甲醛和氢氧根负离子反应的所有可能的反应通道.用6-311++G(3df,3pd)基组对所有的反应中间体、过渡态和产物开展了结构优化和单点能量计算,并经频率分析和内禀反应反应坐标计算(IRC)确认反应物、中间体、过渡态和产物的相关性.在H2CO+OH-所有可能的反应通道中生成CHOO-+H2的通道是该反应的最可几通道,而由于羰基的存在生成H3O-的通道更容易分解产生CHOO-+H2.在高计算水平下计算的氢交换反应结果与文献报道相同.通过计算提出亲核加成过程的反应通道,主要产物生成H2和生成COOH-/HCOO-/OCHO-异构体.所有反应通道的反应几率顺序为COOH-+H2〉H3O-+CO〉HCHO+OH-〉CHO-+H2O〉HCOO-+H2〉O-CHO-+H2.
For the first time, all the possible reaction channels for the reaction of formaldehyde and hydroxide anion were investigated by using the ab initio method at the theoretical level of MP4 (SDTQ). All the reaction intermediates of 6-311 ++ G (3df, 3pd) , Transition states and products were calculated by structural optimization and single-point energy, and the correlations of reactants, intermediates, transition states and products were confirmed by frequency analysis and intrinsic reaction coordinate calculation (IRC) The possible channel for CHOO- + H2 in the reaction channel is the most accessible channel for this reaction, and the channel for H3O- generation due to the carbonyl group is more easily decomposed to CHOO- + H2. Hydrogen exchange reaction calculated at high computational level The results are the same as reported in the literature, and the reaction channel of nucleophilic addition process is proposed by calculation, and the main products produce H2 and form COOH- / HCOO- / OCHO- isomers.The reaction order of all reaction channels is COOH- + H2> H3O - + CO> HCHO + OH-> CHO- + H2O> HCOO- + H2> O-CHO- + H2.