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>OCHO-+H2.

The reaction of formaldehyde (H2CO) with hydroxyl anion (OH-) has been theoretically studied at MP4 (SDTQ) level in conjunction with 6-311++G(3df, 3pd) basis set. All the possible reaction channels are considered for the first time. Geometries of the reactants, intermediates, transition states and products have been optimized. The most favorable reaction channel is found to be H2 molecule production through several paths. Hydrogen symmetric transition in H2CO+OH- is evaluated at higher theory level than literatures. The channel for producing COOH-+H2, contributed from both aldehydic hydrogen abstraction and nucleophilic addition, is the most favorable channel. The Kleingeld-Nibbering reaction channel for producing H3O- is minor, due to the existence of the carbonyl group. The aldehydic hydrogen abstraction for producing H2O, the most dominant channel in the reaction of H2CO+OH, becomes minor in H2CO+OH-. Reaction possibilities of the channels decrease by the following order: COOH-+H2, H3O-+CO, HCHO+OH-, CHO-+H2H, HCOO-+H2 and OCHO-+H2.作者简介：王利.E-mail: liwangye@dicp.ac.cn.通讯作者