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采用半经验的INDO法,首次完成了.α-Keggin结构钼硅四电子杂多蓝K_3H_5[SiMo_4~v-Mo_8~ⅣO_(40)]·12H_2O的量子化学计算.获得了102个成键轨道和68个反键轨道、轨道能级、键序及电荷等数据,证明了杂多酸盐的还原产物杂多蓝,还原后Keggin结构阴离子中各原子上电子云密度重新分配,产生一定程度的结构畸变,但仍保持α一Kegin结构.最高占据轨道由组成分子的各原子轨道组成,其中的桥氧(O_b,O_c)成分较多,表明O_b,O_c为分子中的主要化学活性点.HOMO和LUMO为负值,表明仍可进一步接受电子生成四电子以上的杂多蓝.Muliken分析进一步证明了还原钼原子的位置.
The semi-empirical INDO method was used for the first time to complete the quantum chemical calculation of the four-electron heterosubstituted blue K_3H_5 [SiMo_4-v-Mo_8 ~ ⅣO_ (40)] · 12H_2O with α-Keggin structure. 68 backbones, orbital energy levels, bond order and charge data. It is proved that heteropolyanion, which is the reduction product of heteropolyacid salt, redistributes the electron cloud density of each atom in the Keggin structure anion after reduction, resulting in a certain degree of structure (O_b, O_c), which indicates that O_b and O_c are the main chemical active sites in the molecule.HOMO and LUMO is negative, indicating that the acceptor electron can be further accepted for more than four-electron hybrid heteropoly blue. Muliken analysis further demonstrates the reduction of molybdenum atoms.