若干有机共轭分子二阶非线性光学系数和结构的关系

利用CNDO/S-CI程序计算了四类结构近似的有机共轭分子的二阶非线性光学系数,系统地研究了分子结构、共轭链链长、取代基的电子性质、取代位置等对有机共轭大分子二阶非线性光学性质的影响。研究结果表明,四类化合物的二阶非线性光学性质与其分子结构有着密切的关系。     

一种新的有机非线性光学晶体——L-精氨酸磷酸盐

近年来,在探索新的有机非线性光学晶体的工作中,对含有给电子或受电子基团的芳香族化合物已有广泛深入的研究,并已研制出像2,4-二硝基苯丙氨酸甲酯(MAP)等具有较大倍频系数的新的非线性光学晶体。但是,由于强的共轭效应使它们大π键各能级间的距离接近而使此类晶体无法应用于紫外区。     

具有聚酰胺结构特征的有机非线性光学材料的分子设计

有机非线性光学材料具有非共振系数大,响应时间短,光损伤阈值高等优点,是当前材料科学的重要前沿课题之一,[1-2].目前主要采用改变取代基性质和共轭长度等方法来优化非线性光学极化率和透光性之间的关系[3-4].本文设计了一种新的结构,即在共轭链上含有多个交替排列的供电基团(D)和吸电基团(A),运用量子化学方法研究了这种聚酰胺分子的结构,非线性光学性质和电子光谱,发现它们的非线性光学系数随链长增大,而电子吸收波段并不发生红移.     

有机杂环分子的双光子吸收特性

利用少态模型和密度泛函理论计算了新近合成的三个具有有机杂环结构的苯并噻唑衍生物的非线性光学性质. 计算结果表明，随着有机分子的分子电子离域结构的增大，最大吸收峰红移.当共轭链较长时，共轭链的增长对增强分子双光子吸收截面的影响远大于吸电子基强度变化的影响.该类分子具有较好的双光子吸收特性.最后给出了三个分子的电荷转移过程.     

青年化学教师应重视吸引本科同学参与科研工作 ——成都师范学院青年教师邓国伟博士谈科研与本科生培养

正有机π共轭分子因其特殊的结构、光谱性质和电化学性质等被广泛应用于有机太阳能电池、信息存储材料、传感和非线性光学材料等领域。其中,具有D-π-A结构(D为电子给体,A为电子受体)的发色团分子具有较大的微观一阶超极化率(β),是构筑有机电光材料的重要基团。对发     

对硝基二苯乙炔系列衍生物的二阶非线性光学性质的理论研究

在ZINDO方法基础上,按完全态求和(SOS)公式编制了计算分子二阶非线性光学系数β_ijk和β_μ的程序,研究了对硝基二苯乙炔系列衍生物的结构和非线性光学性质,考察了分子共轭链长和给电子基团对β_μ的影响.结果表明,对硝基二苯乙炔系列衍生物上连有推电子基团有利于增大二阶光学非线性,扩大共轭范围也有利于增大二阶光学非线性,但对透明性则影响不大.     

外缘烷基链长对共轭有机小分子聚集行为及光电性质影响

改变分子化学结构和调控分子结构聚集态行为从而影响或改变材料的化学和物理性质, 是开发新型高效有机光电功能材料的重要手段. 在共轭有机分子外缘引入烷基链一般是为了改进材料溶解性能, 但近来的一些研究表明, 烷基链长对一些共轭有机小分子固态聚集行为和光电性质具有重要影响, 烷基链扮演着显著调控材料光电性质的“功能基团”作用. 本文以聚集诱导发光（aggregation-induced emission, AIE）/聚集强化荧光（aggregation enhanced emission, AEE）发射共轭有机小分子为重点, 对近年来有关烷基链长对共轭有机分子聚集形态和光电性质影响的一些典型事例进行评述, 旨在使人们在进行共轭有机分子设计合成及其结构与性能关系研究中能够关注烷基链的因素, 使烷基链变化作为功能导向晶态共轭有机材料设计合成及其可控制备的一种手段.     

推、拉电子基团对水杨醛缩胺分子电子结构和非线性光学性质的影响

采用量子化学半经验FF／PM3方法,讨论了水杨醛缩苯胺分子中两苯环的对位被推、拉电子基团取代后,体系电子结构和非线性光学性质的变化,考查了分子电子结构对非线性光学性质影响的微观本质,得到的具有给体－共轭桥键－受体型结构的水杨醛缩苯胺分子应显示良好的非线光学性质。     

取代基及共轭链长对共轭多烯二阶线性光学系数影响的量子化学研究

本文采用引入外场微扰的CNDO/S-CI方法, 计算了一系列取代共轭多烯分子的二阶非线性光学系数β~vec, 探讨了 取代基及共轭链长与分子微观非线性光学效应的关系和规律。结构表明:吸电子或供电子基团的引入, 有利于增强分子的微观非线性光学效应, 但该效应随取代基数目增多有减缓的趋势, "饱和"取代时由于"饱和效应"而使β~vec值降低; 取代基间的距离增大, 分子的β~vec值提高, 端基代时β~vec值最大; 取代共轭多烯的lnβ~vec与分子中所含双键数n之间具有线性关系。本文还对上述结论给出了理论解释。     

取代基及共轭链长对共轭多烯二阶线性光学系数影响的量子化学研究

本文采用引入外场微扰的CNDO/S-CI方法, 计算了一系列取代共轭多烯分子的二阶非线性光学系数β~vec, 探讨了 取代基及共轭链长与分子微观非线性光学效应的关系和规律。结构表明:吸电子或供电子基团的引入, 有利于增强分子的微观非线性光学效应, 但该效应随取代基数目增多有减缓的趋势, "饱和"取代时由于"饱和效应"而使β~vec值降低; 取代基间的距离增大, 分子的β~vec值提高, 端基代时β~vec值最大; 取代共轭多烯的lnβ~vec与分子中所含双键数n之间具有线性关系。本文还对上述结论给出了理论解释。     

Zirconium phosphate/phosphonate multilayered films based on push-pull stilbazolium salt: synthesis, characterization and second harmonic generation

The preparation of materials featuring enhanced second harmonic generation (SHG) values by self-assembly of molecules characterized by high second-order non-linear optic (NLO) activity is nowadays an important and challenging field of research. In order to show SHG the material must have an acentric structure with the dipoles of the molecular components oriented in the same direction and this is synthetically fairly difficult to achieve. This study describes the synthesis of the push-pull stilbazolium salt and its assembly in multilayered acentric thin films, on quartz glass surface, by using the zirconium phosphate/phosphonate (Zr-PO(x)) technique. A particular care has been paid to the optimization of the surface preparation and of the deposition conditions. This allows to obtain highly homogeneous lamellar inorganic-organic materials showing satisfactory second harmonic generation (SHG) values together with high chemical, thermal and mechanical stabilities which are necessary for their integration in optoelectronic devices.     

Theoretical and experimental study of optical second harmonic generation in new chiral thiolates salts

The second harmonic generation ability of new chiral thiolate salts is investigated. Aromatic thiolate anions ArS⁻ are expected from semi-empirical calculations with PM3 parameterization of the MNDO Hamiltonian to possess higher intrinsic polarizabilities than the parent neutral thiols ArSH.

Salts associating (hyper)polarizable aromatic thiolate anions with chiral cations, which ensure the noncentrosymmetry necessary to have second-order nonlinear optical effects have been synthesized. The first hyperpolarizabilities, β, of the salts are measured using hyper-Rayleigh scattering technique. Second harmonic generation powder tests (Kurtz and Perry method) carried out on various salts studied, were positive indicating that these materials crystallize in noncentrosymmetric space groups.     

Recent development of the nonlinear optical active material system

New nonlinear optical active materials have been highlighted to apply them to practical applications since about two decades ago. During this period, a number of materials have been developed and studied in academic and industry field. Particularly, the second-order nonlinear optical properties are facile to approach in the laboratory. We can consider the possibility of the device application by investigating the macroscopic second-order nonlinear optical properties using the second harmonic generation and linear electro-optic study. Nowadays, the absolute value of the nonlinear optical coefficient of organic material overcame the value of conventional inorganic materials due to quick research progress. Therefore, the new organic materials systems showed some promising motives to fabricate the optical device.     

Study on second harmonic generation of 9-benzylidene-substituted-10-methyl-9,10-dihydroacridines

Eight 9-benzylidene-substituted-10-methyl-9,10-dihydroacridine derivatives were synthesized from acridine as starting material and were characterized by 1H-NMR, 13C-NMR, Ms and elemental analysis. The second harmonic generation (SHG) values of these compounds were determined in powder using Nd:YAG as a laser source, as compared with urea powder, and the values of second-order polarizabilities (betaxxx), the values of the composite magnitude (betaCTmicrog) of molecular hypersusceptibilities and their moment of these compounds were obtained by the solvatochromic method under ground state for everyone. The results showed that SHG value of 10 is higher than that of urea; the betaCTmicrog of 5 (107.8 x 10(-30) esu) is lower than that of 4-nitro-N,N-dimethylaniline (30 x 10(-30) esu); the betaCTmicrog of 7 (350.8 x 10(-30) esu) and 10 (244.6 x 10(-30) esu) are higher than that of 4-nitro-N,N-dimethylaniline; the betaCTmicrog of 8 (3553 x 10(-30) esu), 11 (1187 x 10(-30) esu) and 12 (1163 x 10(-30) esu) are much more higher than that of 4-nitro-N,N-dimethylaniline. The results demonstrated that this series of compounds possesses good second-order nonlinear optical (NLO) property. The regular relationship could not be obtained between electronegativity of substituents (R) attached to benzylidene ring and SHG values or betaCTmicrog values although the Rs are different in electronegativity and should make an effect on the extent of intramolecular electron-transfer and would consequently influence SHG or betaCTmicrog. The electron-withdrawing ability of R from benzylidene ring played an important role on lambdamax of these compounds.     

Langmuir-Blodgett Film Formation and Optical Second Harmoni Generation of a Hemicyanine Derivative

Langmuir-Blodgett (LB) film of a hemicyanine derivative, (E)-N-hexadecyl-4-[2-(4-dimethylaminophenyl)ethenyl]pyridinium bromide (Hc) was fabricated. The Langmuir film of Hc exhibited good transfer behaviour. Optical second harmonic generation from the LB film was measured. Macroscopic second-order susceptibilily, molecular hyperpolarizability and tilt angle for the molecules on a substrate were estimated to be 7.06×10^-6 esu, 6.47×10^-27 esu,and 31.6° respectively.     

4, 5-二(2', 4'-二硝基苯硫基)-1, 3-二杂环戊烯-2-酮(BNPT-DTO), 4, 5-二(2', 4'-二硝基苯硫基)-1, 3-二杂环戊烯-2-硫酮(BNPT-DTT)分子及晶体激光倍频性质的理论研究

在ZINDO方法的基础上, 按完全态求和公式编制了计算分子的二阶非线性光学系数张量元βijk的程序, 并以此为基础计算了BNPT-DTO, BNPT-DTT分子二次谐波条件下的二阶非线性光学系数, 从分子水平研究了其分子的光学倍频性质及分子倍频与晶体宏观倍频的关系, 计算结果较好地说明了实验现象。     

Second harmonic generation and confined acoustic phonons in highly excited semiconductor nanocrystals

The photo-induced enhancement of second harmonic generation and the effect of nanocrystal shape and pump intensity on confined acoustic phonons in semiconductor nanocrystals have been investigated with time-resolved scattering and absorption measurements. The second harmonic signal showed a sublinear increase of the second-order susceptibility with respect to the pump pulse energy, indicating a reduction of the effective one-electron second-order nonlinearity with increasing electron-hole density in the nanocrystals. The coherent acoustic phonons in spherical and rod-shaped semiconductor nanocrystals were detected in a time-resolved absorption measurement. Both nanocrystal morphologies exhibited oscillatory modulation of the absorption cross section, the frequency of which corresponded to their coherent radial breathing modes. The amplitude of the oscillation also increased with the level of photoexcitation, suggesting an increase in the amplitude of the lattice displacement as well.     

“Small-particle limit” in the second harmonic generation from noble metal nanoparticles

In this paper, we have probed the origin of SHG in copper nanoparticles by polarization-resolved hyper-Rayleigh scattering (HRS). Results obtained with various sizes of copper nanoparticles at four different wavelengths covering the wavelength range 738–1907 nm reveal that the origin of second harmonic generation (SHG) in these particles is purely dipolar in nature as long as the size (d) of the particles remains smaller compared to the wavelength (λ) of light (“small-particle limit”). However, contribution of the higher order multipoles coupled with retardation effect becomes apparent with an increase in the d/λ ratio. We have identified the “small-particle limit” in the second harmonic generation from noble metal nanoparticles by evaluating the critical d/λ ratio at which the retardation effect sets in the noble metal nanoparticles. We have found that the second-order nonlinear optical property of copper nanoparticles closely resembles that of gold, but not that of silver.     

盐酸氨基脲的二阶非线性光学性质研究

非线性光学(NLO)材料在光学信息处理、远程通讯等光电子学领域有着重要的应用,有效地预测和设计出二阶非线性光学材料所必需的非中心对称晶体,提高材料的综合性能是这一领域的研究热点。标题化合物盐酸氨基脲是以尿素为分子母体的有机离子型化合物,具有将有机和无机材料的优异性能集于一身的结构优势,是综合性能优的材料之一。