具有Lindqvist结构的[Mo6O19]^2-化合物及其二钨取代物的电子性质和稳定性的理论研究  

Theoretical Study on Electronic Properties and Stability of [Mo_6O_(19)]^(2-) and Tungsten Substituted Complexes Bearing Lindqvist Structure

作　　者：舒鑫[1] 周欣[1] 潘清江[2] 李明霞[2] 张红星[1] 孙家锺[1] 

机构地区：[1]吉林大学理论化学研究所,理论化学计算国家重点实验室,长春130023 [2]黑龙江大学化学化工与材料学院,哈尔滨150080

出　　处：《高等学校化学学报》2009年第5期1014-1017,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20573042,20703015);黑龙江省自然科学基金(批准号:B200601);黑龙江大学杰出青年基金(批准号:JC2006L2)资助

摘　　要：采用密度泛函理论研究了具有Lindqvist结构的[Mo6O19]2-及其两个钨原子取代化合物的电子性质和稳定性,计算得到的几何数据和实验值符合得很好.从Mulliken电荷分布、键能大小以及轨道性质的分析可以得出结论,当两个钨原子在邻位取代钼原子时所得到的取代产物([4,5-W2Mo4O19]2-)比当两个钨原子在对位取代钼原子时所得到的产物([4,6-W2Mo4O19]2-)更稳定,而[4,5-W2Mo4O19]2-的反应活性比[4,6-W2Mo4O19]2-的大.In order to understand the effects of substituted W atoms on the Mo Lindqvist-type complexes, the electronic properties and stability of the [ Mo6 O19 ]^2- and its two W substituents were investigated via density functional theory （DFT） method at the BP86 functional level. The results are well consistent with the experimental values. According to the analysis of Mulliken population, bond energy and the frontier orbitals, we concluded that the [4,5-W2Mo4O19 ] ^2- is more stable than [4,6-W2Mo4O19 ]^ 2- , however, the [4,5-WEMo4O19]^2- is more active than [4,6-W2Mo4 O19 ]^2-. Our calculations can provide the powerful theoretieal support to the experimental investigation of the Lindqvist complexes.

关 键 词：钼 钨多金属氧化物 键能 密度泛函理论 

分 类 号：O541[理学—物理]