具有不同取代基团的香豆素系列分子二阶非线性光学性质的DFT研究

本文设计了具有不同取代基团的7-苯乙烯基香豆素和4-苯乙烯基香豆素的A、B两个系列共14个化合物分子。采用密度泛函理论B3LYP/6-31G方法对其几何构型进行了全结构优化．在所得优化结构的基础上对这些分子的稳态二阶非线性光学（NLO）系数β值进行计算分析,同时用含时密度泛函理论（TD-DFT）对这些分子的电子性质进行了研究．结果表明：此类香豆素化合物具有较大的分子β值,其中A类分子的共面性好,共轭链长,β值均比B类分子的大．14个化合物中前线分子轨道能级差越小的化合物,其βtot值越大．各分子前线分子轨道跃迁对二阶NLO效应有明显的贡献．     

香豆素衍生物分子二阶非线性光学效应理论研究

用ＣＮＤＯ／Ｓ－ＣＩ程序，计算了了系列香豆素衍生物的分子二阶极化率。从微观上探讨了该类化合物的取代基的电子性质，取代基位置及取代数目对分子二阶极化率的影响。认为取代基的电子性质和取代方式对非线性光学系数有明显的影响。     

含苯乙烯桥侧链三枝分子的二阶非线性光学性质

采用密度泛函理论B3LYP/6-311+g(d,p)方法对含苯乙烯桥侧链均三嗪类衍生物的8个分子(Y1-Y8)进行几何构型优化,对其最优构型采用TD-DFT(TDB3LYP/6-311+g(d,p)),计算电子吸收光谱,用有限场FF方法及自编程序计算二阶非线性光学（NLO）性质。结果表明,8个分子的μ（或0）值为104数量级个原子单位(10-29 esu),显示出良好的二阶非线性光学性能。在其三支链的末端引入强供电子基团（如-N(CH3)2或-N(CH2CH3)2）比引入弱供电子基团及吸电子基团,更有利于改善体系的二阶非线性光学性质,从而可获得良好的非线性光学材料。     

几种香豆素衍生物分子的二阶非线性光学性质的从头算研究

采用从头算ab initio Hartree_Fock/6_31G方法，对以3_苯基香豆素为母体的香豆素系列衍生物分子进行了几何优化，计算了它们的分子二阶非线性光学系数β值，分析了其分子结构、取代基类型和取代位置对β值的影响，并对计算结果所反映的规律性进行了探讨. 关键词： 3_苯基香豆素 非线性光学 二阶效应 从头算 电荷转移     

含亚胺和胆甾烯基液晶分子的电子光谱和二阶非线性光学性质

在B3LYP/6-31G水平上研究了含亚胺和胆甾烯基不对称液晶二聚体的几何结构、电子吸收光谱和二阶非线性光学性质。研究结果表明,该类化合物分子的最强电子跃迁主要源于分子HOMO→LUMO的π→π*跃迁,对应的最大吸收波长位于337~349 nm范围,属于近紫外区。减小分子的中心柔性间隔基的长度和提高端接基的吸电子能力可以增强该类液晶的二阶非光学性质。     

取代基对8-羟基喹啉金属配合物电子光谱和二阶非线性光学性质的影响

在B3LYP/LANL2DZ/6-31G^*水平上优化目标化合物分子的几何结构,并分别在TD- B3LYP/LANL2DZ/6-31++G^**和B3LYP/LANL2DZ/6-31++G^**水平计算目标化合物分子的电子吸收光谱和二阶非线性光学性质.计算结果表明,引入共轭给电子基使配合物分子的最大吸收波长红移,强共轭吸电子基的引入使配合物的最大吸收波长蓝移,取代基的引入使IrQ₃型配合物的二阶非线性光学性质明显增大.对AgQ型配合物,电子跃迁属于配体内部的电荷转移（LLCT）.对PtQ₂和IrQ₃型配合物,电子跃迁属于LLCT和部分金属向配体的电荷转移.取代基对AgQ,PtQ₂,IrQ₃型配合物分子的跃迁性质几乎无影响. 关键词： 8-羟基喹啉金属配合物 电子光谱 二阶非线性光学性质 密度泛函理论     

DFT研究给/吸电子取代基对D-π-A型苯并噻唑衍生物光电性质及非线性光学性质的影响

采用密度泛函理论(DFT)B3LYP方法计算了苯并噻唑及其三种D-π-A型衍生物的电子结构、电子光谱及重组能,同时结合有限场(FF)方法计算了它们的二阶非线性光学系数βtol值,从而探索取代基与分子的电荷分布、电子光谱及非线性光学性质的关系.计算结果显示,在母体分子的2,5位同时引入给/吸电子基团,2位碳原子的电荷布居发生较大变化,且分子的HOMO能级升高,LUMO能级降低,能隙减小,吸收和发射光谱发生显著的红移,增大了二阶非线性光学系数βtol.随着取代基吸电子能力的增强,分子的电子重组能逐渐变大,而空穴重组能的变化却不大,同时分子的偶极矩有所增加,有利于产生二阶非线性光学活性.     

DFT研究给/吸电子取代基对D-π-A型苯并噻唑衍生物光电性质及非线性光学性质的影响

采用密度泛函理论(DFT) B3LYP方法计算了苯并噻唑及其三种D-π-A型衍生物的电子结构、电子光谱及重组能,同时结合有限场(FF)方法计算了它们的二阶非线性光学系数βtol值,从而探索取代基与分子的电荷分布、电子光谱及非线性光学性质的关系。计算结果显示,在母体分子的2,5位同时引入给/吸电子基团,2位碳原子的电荷布居发生较大变化,且分子的HOMO能级升高,LUMO能级降低,能隙减小,吸收和发射光谱发生显著的红移,增大了二阶非线性光学系数βtol。随着取代基吸电子能力的增强,分子的电子重组能逐渐变大,而空穴重组能的变化却不大,同时分子的偶极矩有所增加,有利于产生二阶非线性光学活性。     

α、β-并三噻吩衍生物分子的二阶非线性光学性质

采用密度泛函理论B3LYP/6-31+g(d)方法对二聚α、β-并三噻吩衍生物的18个分子(a～j2) 进行几何构型优化,对其最优构型采用TD-DFT(TDB3LYP/6-31+g(d))计算电子吸收光谱,用有限场FF方法及自编程序计算二阶非线性光学（NLO）性质。计算结果表明,增加共轭链的含乙烯桥的二聚并三噻吩比不含乙烯桥者,µ(或0)大1.6—5.3倍;在含乙烯桥二聚α、β-并三噻吩分子(母体分子) 末端引入含C=C或C≡C的基团（如-C≡CH与-C=C(CN)2）,比引入强供电子基团（如-N(CH2CH3)2）、单纯吸电子基（如F原子）µ(或0) 更大;尤其是端接-C=C(CN)2基团的二聚α、β-并三噻吩衍生物,其µ（或0）值为104数量级个原子单位(10-29 esu),与母体分子相比µ增大4.8～19.6倍,更有利于改善体系的二阶非线性光学性质,从而可获得良好的非线性光学材料。     

α、β-并三噻吩衍生物分子的二阶非线性光学性质

采用密度泛函理论B3LYP/6-31+g(d)方法对二聚α、β-并三噻吩衍生物的18个分子(a~j2)进行几何构型优化,对其最优构型采用TD-DFT(TDB3LYP/6-31+g(d))计算电子吸收光谱,用有限场FF方法及自编程序计算二阶非线性光学(NLO)性质。计算结果表明,增加共轭链的含乙烯桥的二聚并三噻吩比不含乙烯桥者,βμ(或β0)大1.6—5.3倍;在含乙烯桥二聚α、β-并三噻吩分子(母体分子)末端引入含C=C或C≡C的基团(如-C≡CH与-C=C(CN)_2),比引入强供电子基团(如-N(CH_2CH_3)_2)、单纯吸电子基(如F原子)βμ(或β0)更大;尤其是端接-C=C(CN)2基团的二聚α、β-并三噻吩衍生物,其βμ(或β0)值为104数量级个原子单位(10-29esu),与母体分子相比βμ增大4.8~19.6倍,更有利于改善体系的二阶非线性光学性质,从而可获得良好的非线性光学材料.     

溶剂中一、二维电荷转移分子二阶非线性光学性质理论研究

以典型的一、二维电荷转移分子,对硝基苯胺(pNA),1,3-二氨基-4,6-二硝基苯(DADB)分子为例,运用密度泛函理论(DFT)B3LYP和含时耦合微扰(TDHF)方法在6-31+G(d,p)水平上研究了溶剂和入射光频率对目标分子的非线性光学性质的影响.研究发现溶剂分子对分子一阶超极化率β和紫外吸收光谱的影响很大,但对一阶超极化率各向异性比η和退偏比D的影响很小,这是由于随着溶剂相对介电常数的增加,一阶超极化率的分量︱βxxy︱和︱βyyy︱不断增加,且二者具有很好的线性相关性.然而,考虑色散效应后,不同溶剂中分子的一阶超极化率及其各向异性参数都不相同,色散效应对分子一阶超极化率及其各向异性性质均有很大影响.考虑溶剂效应和色散效应后得到的计算结果与实验结果符合得较好.     

足球烯分子三阶非线性光学性质的研究

报道了有关足球烯分子甲苯溶液中简并四波混频实验.测量出足球烯C_(70)分子和C_(60)分子的三阶超极化率张量y_(1111)分量分别为1.2×10~(-30)esu和4.0×10~(-31)esu.对应于固体样品的三阶非线性光学系数X_(1111)分量分别是2.5×10~(-8)esu和8.5×10~(-9)esu.此结果表明了足球烯分子是现有的非线性光学材料中具有较大三阶非共振电子极化率材料之一.文中还利用自由电子模型解释了非线性光学极化率的起源.     

Studies of the second-order nonlinear optical properties of cubic boron nitride

Cubic boron nitride (cBN) is a kind of artificial wide-energy-gap semiconductor crystal, which has zinc blende structure with Td symmetry. The second-order nonlinear optical properties of cBN single crystal were investigated for the first time. Using a Q-switching Nd:YAG laser, the optical rectification and the second-harmonic generation at 532 nm from cBN single crystal were observed. In order to determine the nonlinear optical coefficient of a minute-size cBN sample, a simple method based on modified transverse linear electro-optic modulation was also introduced. This approach is convenient because it is unnecessary to know the absolute intensity of a probing beam for measuring the half-wave voltage of a cBN sample. Finally, cBN’s linear electro-optic coefficient γ₄₁=1.07×10^-14 m/V and nonlinear optical coefficient d₁₄(0,ω,-ω)=1.07×10^-13 m/V were obtained. PACS 42.65.An; 42.65.Ky; 78.20.Jq     

Electric field effect on the second-order nonlinear optical properties in semiparabolic quantum wells

Electric field effect on the second-order nonlinear optical properties in semiparabolic quantum wells are studied theoretically. Both the second-harmonic generation susceptibility and nonlinear optical rectification depend dramatically on the direction and the strength of the electric field. Numerical results show that both the second-harmonic generation susceptibility and nonlinear optical rectification are always weakened as the electric field increases where the direction of the electric field is along the growth direction of the quantum wells, which is in contrast to the conventional case. However, the second-harmonic generation susceptibility is weakened, but the nonlinear optical rectification is strengthened as the electric field increases where the direction of the electric field is against the growth direction of the quantum wells. Also it is the blue (or red) shift of the resonance that is induced by increasing of the electric field when the direction of the electric field is along (or against) the growth direction of the quantum wells. Finally, the resonant peak and its corresponding to the resonant energy are also taken into account.     

Redox and photoisomerisation switching the second-order nonlinear optical properties of a tetrathiafulvalene derivative across ten stable states: a DFT study

A molecular switch having large contrast on the second-order nonlinear optical (NLO) properties has been studied based on tetrathiafulvalene (TTF)-π-polynitrofluorene (PTF) molecule. It can afford to switch second-order NLO response across 10 stable states by an effective combination of its photoisomerisation and redox properties. According to density functional theory (DFT) finite field calculations (BHandHLYP/CAM-B3LYP/LC-BLYP/6-31g(d)), the redox-active TTF, TCNQ (7,7′,8,8′-tetracyano-p-quinodimethane) units, and a photoisomerised chromophore (thiophene derivative of perfluorocyclopentene) act as the tuning centre to switch second-order NLO responses. Meanwhile, time-dependent DFT method has been employed to calculate excited-state nature for getting more insights of the second-order NLO responses.     

Dispersion of second-order nonlinear optical coefficient

A simple, approximate relation between the dispersion of the second-order nonlinear optical (SNLO) coefficient and first-order susceptibility has been derived using the well-known results of density-matrix calculation of quantum-mechanical theory. A new tensor of SNLO coefficient has been defined, which retains symmetries when the input beams are in the spectral range of transparency while the generated beam can also be in the spectral range of absorption. The validity of the relation has been checked for three ferroelectric crystals, KTP, LiNbO₃ and KNbO₃, which are transparent in the visible and near infrared, and for two semiconductors, GaP and GaAs, which absorb in the visible. Contrary to Miller’s law, the presented relation is in good agreement with measurements. Received: 8 February 2001 / Revised version: 2 July 2001 / Published online: 10 October 2001     

二维电荷转移分子非线性光学性质的理论研究

运用密度泛函理论B3LYP方法在6-31+G（d,p）水平上计算了11个X型二维电荷转移分子的电荷分布、紫外吸收光谱、第一超极化率.结果表明：在x或y方向延长共轭体系,最大吸收波长 红移,第一超极化率 增大,并且在y方向延长共轭体系,能够较好的优化分子透明性与分子非线性光学性质,获得兼具大 和良好透光性的非线性光学性能好的分子;另外,杂原子N取代芳香环上的C原子的位置和数目对分子非线性光学性质有重要影响.