使用相对论赝势从头计算方法和成键能判据研究了模型化合物ＭＣＯ和ＭＣＯＮａ＋（Ｍ＝Ｆｅ，Ｎｉ）分子的电子结构，讨论了Ｍ对ＣＯ分子的活化作用及Ｎａ＋的助活化作用．由分子轨道成键能分析指出ＣＯ的次最高占据分子轨道１的消弱是使ＣＯ活化的关键，得出在模型化合物ＭＣＯＮａ＋（Ｍ＝Ｆｅ，Ｎｉ）中Ｎａ＋的引人消弱了ＣＯ的１轨道的成键强度，Ｎａ＋的助催化作用是通过电荷而非通过化学键实现的． The electronic structures of MCO and MCONa + (M = Fe, Ni) molecules were investigated using ab initio method and bond energy criterion of relativistic pseudopotential. The activation of CO and the co-activation of Na were discussed. The analysis of molecular orbital bonding energies indicates that the weakening of the sub-highest occupied molecular orbit 1 of CO is the key to CO activation. It is concluded that the introduction of Na + in the model compound MCONa + (M = Fe, Ni) attenuates 1 Orbital bond strength, Na + cocatalytic effect through charge rather than through chemical bonds.