Second-Order Nonlinear Optical Responses of AlN Two-Dimensional Monolayer: A Real-Time First-Principles Study

Two-dimensional materials have recently attracted attention due to their unique physical properties and promising applications. This work reports the electronic, linear and second-order nonlinear optical properties of aluminum nitride (AlN) monolayer by using a real-time first-principles approach based on Green's function theory. In this approach, quasi-particle corrections, crystal local field effects, and excitonic contributions are considered for investigating the linear and nonlinear responses. As a two-dimensional material with a wide direct gap of around 6.45 eV, the AlN monolayer exhibits strong resonances of absorption and second-harmonic spectra in the ultraviolet range. In the transparent spectral range from blue to deep ultraviolet (2.8–5.3 eV), strong peaks of second-order nonlinear susceptibility appear in the AlN monolayer with a large peak value of around 430 pm/V, which is one or two orders-of-magnitude larger than the nonlinear materials used in the ultraviolet range. The results presented in this work will find important applications for nonlinear imaging, spectroscopy, and nonlinear nanophotonics in the ultraviolet range.     

二阶非线性光学特性聚氨酯研究进展

非线性光学聚氨酯的研究引进国内外学者的广泛关注,有些体系已经发展到可以制成实验室模型器件。综述了近年来采用聚氨酯为骨架材料的二阶非线性光学聚合物材料的研究进展情况,展望了今后的研究方向。     

吡啶二亚胺过渡金属配合物的二阶非线性光学性质

采用密度泛函理论(DFT) B3LYP方法,对8个吡啶二亚胺配合物的几何结构、电子光谱和二阶非线性光学(NLO)性质进行了计算和分析.结果表明,配合物的极化率受副配体和中心金属离子的影响不大,副配体对配合物二阶NLO系数的影响也不明显.随金属离子d电子数的增加,配合物二阶NLO系数(β)有所减小,同一族金属离子随半径增大,其配合物相应的βtot值增加.配合物中的金属离子起到供电子作用时,配合物最大振子强度下的跃迁能较小,其相应的βtot值较大.     

含有Pt―Pt键金属配合物的电子结构和二阶非线性光学性质

采用量子化学密度泛函理论(DFT)结合有限场(FF)的方法对一系列含有Pt―Pt键金属配合物的电子结构和二阶非线性光学(NLO)性质进行了理论计算. 结果表明改变共轭配体对Pt―Pt键影响不大. 由配体到Pt―Pt金属基团的电荷转移强度随配体增长而变大. 金属配合物静态一阶超极化率随配体的增长而增大, 配合物电荷的改变基本不影响这类化合物的二阶NLO性质. 具有相对长的共轭配体的配合物IId具有最大的二阶NLO响应. 含时密度泛函理论(TD-DFT)计算表明配合物IId的二阶NLO响应来自于混有配体到金属的配体内的π→π^*电荷转移跃迁的贡献.     

有机二阶非线性光学发色团的研究进展

近年来,科学家们通过引进杂环片段、采用双(或多)官能化以及运用分子间弱相互作用等方法,在二阶非线性光学发色团的性能优化方面取得了较大进展.结合本课题组的研究,对此领域的研究进行了较全面的综述,并特别针对“非线性-透光性”矛盾的解决途径进行了较为详细的介绍.     

偶氮香豆素化合物的二阶非线性极化率

测定了一系列偶氮香豆素化合物的紫外吸收波长(λ_a)、摩尔吸光系数(ε)和最大荧光发射波长(λ_e)的数据,并用溶致变色法测算了它们的二阶非线性极化率(β_xxx).结果表明,所测定的化合物在溶液状态下表现出较强的二阶非线性极化特性.     

Formation of Transient Anionic Metal Clusters in Palladium/Diene-Catalyzed Cross-Coupling Reactions

Despite their considerable practical value, palladium/1,3-diene-catalyzed cross-coupling reactions between Grignard reagents RMgCl and alkyl halides AlkylX remain mechanistically poorly understood. Herein, we probe the intermediates formed in these reactions by a combination of electrospray-ionization mass spectrometry, UV/Vis spectroscopy, and NMR spectroscopy. According to our results and in line with previous hypotheses, the first step of the catalytic cycle brings about transmetalation to afford organopalladate anions. These organopalladate anions apparently undergo S_N2-type reactions with the AlkylX coupling partner. The resulting neutral complexes then release the cross-coupling products by reductive elimination. In gas-phase fragmentation experiments, the occurrence of reductive eliminations was observed for anionic analogues of the neutral complexes. Although the actual catalytic cycle is supposed to involve chiefly mononuclear palladium species, anionic palladium nanoclusters [Pd_nR(DE)_n]⁻, (n=2, 4, 6; DE=diene) were also observed. At short reaction times, the dinuclear complexes usually predominated, whereas at longer times the tetra- and hexanuclear clusters became relatively more abundant. In parallel, the formation of palladium black pointed to continued aggregation processes. Thus, the present study directly shows dynamic behavior of the palladium/diene catalyst system and degradation of the active catalyst with increasing reaction time.     

Theoretical Investigation of Second-Order Nonlinear Optical Properties of Substituted Benzothiazole Derivatives

On the basis of the ZINDO program, we have designed a program to calculate the nonlinear second-order polarizabilities _ijk, ₀, and according to the SOS expression. The second-order nonlinear optical properties of a series of benzothiazole derivatives including 2-(p-donor--styryl)-6-nitrobenzothiazole, 2-(p-donor-phenyl)-azo-6-nitrobenzothiazole, and 2-(p-nitro--styryl)-6-donor-benzothiazole derivatives were studied. The calculated results show that when the benzothiazole rings are connected to the nitro group (acceptor), the values are relatively larger. This does not agree with the theory of auxiliary donor–acceptor effects. The 2-(p-donor--styryl)-6-nitrobenzothiazole derivatives exhibit more nonlinearity than 2-(p-donor-phenyl)-azo-6-nitrobenzothiazole derivatives. The 2-(p-donor--styryl)-6-nitrobenzothiazole derivatives are good candidates as chromophores due to their high nonlinearities and good thermal stability.     

Second-Order Nonlinear Optical Properties of a Polymer Exhibiting Optical Transparency Down to 340 nm

Abstract

The synthesis and characterization of an epoxy-based nonlinear optical (NLO) polymer exhibiting optical transparency down to 340 nm is reported. The synthesized polymers show spectroscopic properties (NMR, IR, UV) in accordance with the proposed structures. A glass transition temperature (T_g) of 92°C and a thermal degradation temperature (T_d) of 322°C were recorded. The poled polymer film exhibits stable second-order nonlinear optical activity (d₃₃ = 4.2 pm/V) over a period of 800 hours as characterized by the temporal response of the second harmonic signal at room temperature.     

从多羟基低聚物出发合成交联型二阶非线性光学聚合物

从多羟基低聚物出发合成交联型二阶非线性光学聚合物王全伏景遐斌＊王化滨汪冬梅韩孝族（中国科学院长春应用化学研究所高分子物理联合开放实验室长春１３００２２）关键词羟基低聚物，非线性光学，交联聚合物，合成１９９７－０３－２８收稿，１９９７－０８－０８修回国...     

关于二阶非线性光学性质的分子设计研究

在INDO/CI基础上,用完全态求和公式自编程序计算二阶非线性光学系数β_ijk,考察了分子骨架、受电子基团或给电子基团变化对β_x的影响,并设计了最大β_x的化合物、计算结果均与实验值相符。     

含咔唑生色团的有机芳香杂环分子的二阶非线性光学性质

采用密度泛函理论B3LYP/6-31G^*方法, 对一系列含咔唑生色团的有机芳香杂环分子进行结构优化, 并采用有限场(FF)和含时密度泛函理论(TD-DFT)方法在6-311G^**水平上探讨了体系的二阶非线性光学(NLO)性质和电子光谱. 结果表明, 咔唑取代基推或拉电子能力的改变和引入芳香杂环对研究分子的极化率α和二阶NLO系数β值都有较大影响. 当取代基分别连有拉电子硝基和推电子羟基, 以及引入呋喃杂环都可以使体系分子的β值随分子的最大吸收波长λ_max的增大而减小(蓝移). 该系列化合物兼具有很大的二阶非线性响应与良好的透光范围, 避免了“非线性-透光性”矛盾, 可能在非线性材料领域中有很大的潜在应用价值.     

两类非线性光学性质稳定的交联极化聚合物

报道了两类新型含对硝基苯偶氮苯胺发色团的热交联型二阶非线性光学聚合物的合成和极化工艺，双端丙为烯酸酯的分解红（ＤＲ）－１９热聚合合生成交联型聚丙烯酸酯；双端苯酚封闭异氰酸酯端基的ＤＲ－１９与含多羟茏牟（丙烯酸－β－羟丙酯－ＤＲ－１－ＭＡＳ）共聚物反应生成交联聚氨酯，ＤＳＣ测得两者的玻璃化转变温度为１２５℃和１６０℃，旋转涂膜后在１６０℃电晕极化１ｈ可制得良好光学性质的极化膜，采用可见光吸收光谱测定     

Optical Properties of Noble Metal Clusters in Ultrathin Solid Films

We report on the optical properties (absorption, Raman response) of thin and ultrathin phthalocyanine and amorphous silicon films with incorporated noble metal clusters. The metal clusters cause the typical absorption features originating from their surface plasmon resonance. In ultrathin films, due to the spatially close interface, the plasmon absorption may be displaced from its resonance frequency in the bulk, and its average position may be controlled by the average thickness of the ultrathin optical film. For example, we observe a shift of the plasmon resonance of silver clusters in amorphous silicon films (on fused silica) from 440 nm to 740 nm, when the silicon thickness increases from zero up to 9 nm. The deposition experiments are accompanied by investigations of the film structure, particularly in order to estimate the silver cluster diameter, which is around 3 nm or less.     

双环金属铱(Ⅲ)异腈配合物的二阶非线性光学性质

采用密度泛函理论(DFT)方法对双环金属Ir(III)异腈配合物的非线性光学(NLO)性质进行计算研究。用B3PW91(UB3PW91)(金属原子采用LANL2DZ基组,非金属原子采用6-31G*基组)方法对配合物进行几何结构优化。在优化构型基础上,采用B3PW91(UB3PW91)和B3LYP(UB3LYP)方法计算了配合物的第一超极化率(βtot),并用CAM-B3LYP(UCAM-B3LYP)(金属原子采用LANL2DZ基组,非金属原子采用6-31G**基组)方法模拟配合物的吸收光谱。结果表明,主配体的取代基(R1)和副配体的取代基(R2)对第一超极化率值贡献不大。配合物发生氧化还原反应,电荷转移方式增多,电荷转移程度增大,使βtot值显著增加,其中1a+([(C∧N)2Ir(CNR)2]+(R=CH3))发生氧化反应和还原反应的βtot值分别增大了75倍和144倍。因此,这类双环金属铱(III)异腈配合物的氧化还原反应可以有效地调节其二阶NLO性质。     

手性联萘桥联双卟啉的电子光谱与二阶非线性光学性质

在6-31G(d,p)水平上用B3LYP方法对手性联萘桥联双卟啉系列分子进行几何构型优化. 用半经验ZINDO/S方法计算了这些分子的电子光谱, 结果表明手性联萘桥联双卟啉中两个卟啉生色团之间存在强的激子耦合作用, B带的Davydov分裂大小与两个卟啉环的相对取向以及卟啉环中心之间距离有关. 用ZINDO/SOS方法计算了分子的一阶超极化率. 卟啉环上引入推/拉电子基团可以有效地提高手性联萘桥联双卟啉的二阶非线性光学系数. 一阶超极化率的大小与双卟啉中推/拉电子基团的空间排列方式有关. 一阶超极化率的提高不仅与分子激发态与基态偶极矩差增大有关, 还和基态偶极矩与激子耦合激发态跃迁矩矢量的相对取向密切相关.     

Mechanistic Insights into Statistical Co-Assembly of Metal Complexes

Statistical copolymerization plays a key role in many biological and technological processes; however, mechanistic understanding of the formation of analogous supramolecular counterparts remains limited. Herein, we report detailed insights into the supramolecular co-assembly of two π-conjugated Pd^II and Pt^II complexes, which in isolation self-assemble into flexible fibers and nanodisks, respectively. An efficient single-step co-assembly into only one type of nanostructure (fibers or nanodisks) takes place if any of the components is in excess. In contrast, equimolar mixtures lead to Pd^II-rich fiber-like co-assemblies by a statistical co-nucleation event along with a residual amount of self-sorted nanodisks in a stepwise manner.     

一种激光倍频新材料──间羟基苯甲酸的初步研究

二阶非线性光学(NLO)材料又称为倍频材料,在光电子学领域中具有广泛的应用,是近年来研究热点之一[1～4].与无机材料相比,由于有机倍频材料具有非线性光学系数大、响应时间短和抗光伤阈值高等优异性能而倍受人们的关注.但有机材料在透光性能、热稳定性和材料的可加工性方面不及无机材料,使之应用受到很大限制.因而有效地解决这一问题是其得以广泛应用的关键.对于有机倍频材料来说,优化材料综合性能的关键在于保持有机材料优良性能的基础上提高化合物的透光性和热稳定性.有机化合物的分子间氢键和两性离子对改善NLO材料的热稳定性和牢固性…     

Inclusion Crystals of Cedrol and Phenol-type of Compounds for Second-Order Nonlinear Optical Application

This present paper reports that the cedrol and phenol-type of inclusion crystals exhibit SHG effect. These inclusion crystals with noncentrosymmetrical structure possess lower cutoff wavelength(290-380 nm) and higher reflection rate (300-1200 nm), and show a great promising application prospect.