高等学校化学学报

高等学校化学学报

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双核金属茂合物Zn2(η5-E5)2(E=N, P, As, Sb)电子结构和三阶非线性光学性质的理论研究

赵树魁1, 孙秀云1, 方亮2, 朱玉兰3   

    1. 吉林化工学院数理学院, 吉林 132022;
    2. 东北师范大学化学学院功能材料化学研究所, 长春 130024;
    3. 淮阴师范学院化学系, 淮安 223001
  • 收稿日期:2007-01-28 修回日期:1900-01-01 出版日期:2007-09-10 发布日期:2007-09-10
  • 通讯作者: 孙秀云

Theoretical Studies on Electronic Structures and Third-order Nonlinear Optical Properties of Di-metallocene Complexes Zn2(η5-E5)2(E=N, P, As, Sb)

ZHAO Shu-Kui1, SUN Xiu-Yun1*, FANG Liang2, ZHU Yu-Lan3*   

    1. School of Science Jilin Institute of Chemical Technology, Jilin 132022, China;
    2. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China;
    3. Department of Chemistry, Huaiyin Teachers College, Huai'an 223001, China
  • Received:2007-01-28 Revised:1900-01-01 Online:2007-09-10 Published:2007-09-10
  • Contact: SUN Xiu-Yun

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摘要： 运用密度泛函PBE0方法研究了双核金属茂合物Zn2(η5-E5)2(E=N, P, As, Sb)的电子结构, 运用自然键轨道(NBO)方法对该体系的电荷分布及成键特征进行了分析. 此类体系中存在Zn—Zn的σ单键, 为近似纯s成分的成键方式. 用含时密度泛函理论(TDDFT ) 完全态求和(SOS) 方法计算了该体系的三阶非线性光学系数, 结果表明, γ值与最大吸收波长λmax成正比, 在各个分量中, 对〈γ〉起主要贡献的是γzzzz, 最大吸收波长对应的电子跃迁是从Zn—Zn的σ成键轨道到Zn—Zn的σ*反键轨道.

关键词: 双核金属茂合物, 非线性光学性质, 自然键轨道, 含时密度泛函理论, 态求和方法

Abstract: Electronic structures of di-metallocene complexes Zn2(η5-E5)2(E=N, P, As, Sb) were investigated with DFT PBE0 method. Charge distribution and bonding characters are analyzed with Natural Bond Orbital(NBO) Theory. The results show that a single σ-bond of Zn—Zn exists in these complexes with a nearly pure s character. The nonlinear third-order polarizabilities(γ) were calculated for the four di-metallocene complexes by time-dependent density functional theory(TD-DFT ) combined with sum-over-states(SOS) method. The calculated results show that γ value is in direct proportion to the maximum absorption wavelength(λmax). Analysis of the main contributions to the third-order polarizability suggests that electron transfer(Zn—Zn σ-bond →Zn—Zn σ*-bond ) along z-axis direction plays a key role in the nonlinear optical response.

Key words: Di-metallocene complexes, NLO property, NBO, TD-DFT, SOS method

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