α和β构型八钼酸根的理论研究  

Theoretical studies on isomers of α-and β-[Mo_8O_(26)]^(4-)

作　　者：唐典勇[1] 刘雪梅[1] 李蓉[1] 

机构地区：[1]乐山师范学院化学与生命科学学院分子设计中心,四川乐山614000

出　　处：《化学研究与应用》2012年第3期365-369,共5页Chemical Research and Application

基　　金：四川省教育厅资助项目(No.10ZA033);乐山师范学院青年教师启动项目

摘　　要：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 α-and β-Mo8O264-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 α and β-Mo8O264-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-O interactions have been found to be predominantly 4d（Mo）-sp3（O）in character.The oxidation behavior of α-and β-Mo8O264-is very nearly the same,which is in agreement with the catalytic activity of thioether oxidation.

关 键 词：八钼酸根 密度泛函理论 自然键轨道分析 总态密度 氧化性 

分 类 号：O643.12[理学—物理化学]