在 HF,B3LYP和 QCISD(T)水平上研究了 HCO+和 HOC+与 C2 H2 的气相质子转移反应 .结果表明 :高级电子相关效应对研究质子转移过程极为重要 ;HCO+和 HOC+通过质子垂直进攻 C2 H2 的 π-键分别生成中间体 OC· HC2 H+2 和 CO· HC2 H+2 ,最终生成主要产物为π-质子化的乙炔 HC(H) CH+;对于质子转移反应 HOC+比 HCO+更为活泼 .计算结果与实验结果符合得较好 ,这将有助于理解星际化学以及燃烧化学中的质子转移过程 The gas-phase proton transfer reactions of HCO + and HOC + with C2H2 were studied at HF, B3LYP and QCISD (T) levels. The results showed that the advanced electron-related effects were very important for the study of proton transfer processes; HCO + and HOC + π-bond to generate the intermediates OC · HC2 H + 2 and CO · HC2 H + 2, respectively, finally producing acetylene HC (H) CH + with the main product π-protonation; HOC + is more active than HCO + for the proton transfer reaction The results are in good agreement with the experimental results, which will help to understand the processes of interstellar chemistry and proton transfer in combustion chemistry