基于多酸化合物氧化还原性质的开关 NLO 响应的理论探索 [XNbWO]（X=Al、Si、P、S、Ga、Ge、As、Se）。
Theoretical exploration on switchable NLO response induced by redox properties of polyoxometalates [XNbWO] (X = Al, Si, P, S, Ga, Ge, As, Se).
机构信息
Scientific Instrument Center, Shanxi University, Taiyuan 030006, China.
Institute of Functional Material Chemistry, Key Laboratory of Polyoxometalate Science of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China.
出版信息
J Mol Graph Model. 2018 May;81:155-161. doi: 10.1016/j.jmgm.2018.02.019. Epub 2018 Mar 2.
Calculations based on density functional theory (DFT) have been performed to investigate the relationship between redox properties and second-order nonlinear optical (NLO) responses of Keggin-type anions [XNbWO] (X = Al, Si, P, S, Ga, Ge, As, Se) and their corresponding heteropoly blues. The frontier molecular orbitals, NLO responses and electronic transition properties of fully oxidized anions and heteropoly blues were discussed. It is noticeable that the second-order NLO behaviors can be switched by reduced electrons for these Keggin-type anions. The calculated β value of heteropoly blues [XNbWO] (X = P, As, S) are 21-23 times as large as those of fully oxidized anions [XNbWO] (X = P, As, S) according to CAM-B3LYP/6-31G* (LANL2DZ basis sets for metal atom) calculations in CHCN. The aim of this work is to combine the attractive redox properties and NLO response of polyoxometalates to obtain the switchable NLO materials.
基于密度泛函理论（DFT）的计算已被用于研究 Keggin 型阴离子[XNbWO]（X=Al、Si、P、S、Ga、Ge、As、Se）及其相应的杂多蓝的氧化还原性质和二阶非线性光学（NLO）响应之间的关系。讨论了完全氧化的阴离子和杂多蓝的前沿分子轨道、NLO 响应和电子跃迁性质。值得注意的是，对于这些 Keggin 型阴离子，通过减少电子可以切换二阶 NLO 行为。根据在 CHCN 中使用 CAM-B3LYP/6-31G*（金属原子的 LANL2DZ 基组）计算，杂多蓝[XNbWO]（X=P、As、S）的β值是完全氧化的阴离子[XNbWO]（X=P、As、S）的 21-23 倍。这项工作的目的是结合多金属氧酸盐的吸引人的氧化还原性质和 NLO 响应，以获得可切换的 NLO 材料。
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