本文用考虑了零级微扰近似相对论效应的RI-TPSS/def2-SVP方法计算了八钼酸根的α和β两种异构体的几何结构.然后在TPSSh/def2-TZVPP水平(考虑了ZORA相对论效应)下计算了相关电子性质并进行了自然键轨道分析和总态密度分析.ZORA-RI-TPSS/def2-SVP水平能非常好的重复晶体结构.分子的负电荷分布到体系中的各个氧原子上,并且氧原子配位数越大,其带负电荷就越大.Mo-O键主要由Mo的4d轨道与O的sp3杂化轨道重叠形成.α和β构型的八钼酸根的氧化性相差不大,与八钼酸根催化硫醚氧化反应实验结果是一致的.%Molecular structures of a-and β-MogO26 4- were investigated at the RI-TPSS/def2-SVP level in the gaseous phases with full geometry optimization including the relativistic zeroth-order regular approximation(ZORA). Then,the electronic properties,natural bond orbital(NBO)analysis,and total density of state(TDOS)analysis were performed at the TPSSh/def2-TZVPP(ZORA)level. The optimized geometry structures of a and β-MogO26 4- are in good agreement with that of X-ray. The negative charge is distributed over all types of oxygen atoms, and the individual values are observed to increase with the coordination number. All Mo-0 interactions have been found to be predominantly 4d(Mo)-sp3 (O)in character. The oxidation behavior of a-and β-MogO26 4- is very nearly the same,which is in agreement with the catalytic activity of thioether oxidation.
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