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采用SCC-DV－Xα方法对α－Keggin结构四电子还原态杂多蓝阴离子[SiMo4VMo8VIO40]8-及其四钒取代阴离子[SiMo4VMo8VIO40]8-进行了量子化学计算研究，获得了轨道能级、费米能级、各原子价电子布居，自由价，总态密度图和自洽原子轨道布居等信息．分析表明杂多阴离子中Oc和Od的成键能力较强，化学活性较大，这有力支持了实验结果．体系各原子上的电子是以离域形式存在，构成三金属簇的八面体结构都发生一定程度畸变，中心的硅氧四面体发生畸变程度很小，但整体仍保持α-Keggin结构．
The quantum chemical calculations of the tetrakis-vanadium-substituted anions [SiMo4VMo8VIO40] 8- and tetrakis-anions of [SiMo4VMo8VIO40] 4- in the α-Keggin structure were carried out using the SCC-DV-Xα method. M level, atomic valence electron population, free valence, total state density map and self-consistent atomic orbit population. The analysis shows that Oc and Od in heteropolyanions have stronger bonding ability and higher chemical activity, which strongly supports the experimental results. The electron of each atom in the system exists in the form of delocalization. The octahedral structure of the three metal clusters is distorted to a certain degree. The distortion of the center of the silicon tetrahedron is very small, but the α-Keggin structure remains.