Yan Likai, Yang Guochun, Guan Wei, Su Zhongmin, Wang Rongshun
Institute of Functional Material Chemistry, Department of Chemistry, Northeast Normal University, Changchun 130024, People's Republic of China.
J Phys Chem B. 2005 Dec 1;109(47):22332-6. doi: 10.1021/jp0542120.
The first hyperpolarizabilities and origin of nonlinear optical (NLO) properties of arylimido molybdate derivatives have been investigated by density functional theory (DFT). The molecular orbital character analysis reveals that organoimido-to-polyanion charge transfer may be responsible for the NLO properties of this kind of molybdate derivatives. The NLO study shows intra-ion charge transfer is helpful to increase the first hyperpolarizability of arylimido molybdate derivatives. The lengthening of organoimido pi-conjugation enhances the betavec value. System 4 has the largest betavec value at the static electronic field, 1.238 x 10(-27)esu. Orbital analysis shows that the degree of charge transfer between polyanion cluster and organic segment was increased when the second organoimido polyanion was introduced. The present investigation provides important insight into NLO origin and properties of polyanion arylimido molybdate derivatives.
采用密度泛函理论（DFT）研究了芳基亚氨基钼酸盐衍生物的一阶超极化率及非线性光学（NLO）性质的起源。分子轨道特征分析表明，有机亚氨基到聚阴离子的电荷转移可能是这类钼酸盐衍生物NLO性质的原因。NLO研究表明，离子内电荷转移有助于提高芳基亚氨基钼酸盐衍生物的一阶超极化率。有机亚氨基π共轭的延长增强了β值。体系4在静电场下具有最大的β值，为1.238×10^(-27) esu。轨道分析表明，当引入第二个有机亚氨基聚阴离子时，聚阴离子簇与有机片段之间的电荷转移程度增加。本研究为聚阴离子芳基亚氨基钼酸盐衍生物的NLO起源和性质提供了重要的见解。
