双核金属茂合物Zn_2(η~5-E_5)_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  

Theoretical Studies on Electronic Structures and Third-order Nonlinear Optical Properties of Di-metallocene Complexes Zn_2(η~5-E_5)_2 (E=N,P,As,Sb)

作　　者：赵树魁[1] 孙秀云[1] 方亮[2] 朱玉兰[3] 

机构地区：[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

出　　处：《高等学校化学学报》2007年第9期1731-1734,共4页Chemical Journal of Chinese Universities

基　　金：吉林省科技厅'分子模拟技术在催化中的应用'项目(批准号:20030119)资助.

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.Electronic structures of di-metallocene complexes Zn2 （η^5-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 y value is in direct proportion to the maximum absorption wavelength （Amax）. 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.

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 

分 类 号：O641[理学—物理化学]