中文摘要：

采用密度泛函方法B3LYP／6—311＋＋G（d，p）研究了亚硝基苯C6H5-N=0和2-甲基-2-亚硝基丙烷（CH3）3C—N=0与甲醛分别在气相和溶剂中的反应机理．在气相中均找到两条反应通道，即协同机理和分步机理，均生成实验产物氧肟酸，而且分步机理均为优势通道；除2-甲基-2-亚硝基丙烷的反应没有协同途径外，在溶剂中反应机理与气相中的类似．采用导电极化连续介质模型分别研究了在乙腈与水溶液中反应的溶剂化效应，发现这些溶剂可降低反应的活化能，但降低的程度比较小，反应速率变化不大．

英文摘要：

The DFT method B3LYP/6-311 ＋ ＋ G（d,p） was used to study mechanism of reactions of nitrosobenzene and 2-methyl-2-nitrosopropane with formaldehyde in gas phase and solvents. In gas phase, there are two reaction paths, the concerted and stepwise mechanisms, both of which produce the experimental product, hydroxamic acid; the stepwise mechanism is predominant. The solvent effects were studied with the conductorlike polarizable continuum model respectively in the solvents acetonitrile and water, and we found that the solvent effects reduce the activation energy, but the reduction is small, these reactions are not sensitive to the solvent polarity.