激发态分子内质子转移有机分子HBT的三阶非线性光学特性

以532nm皮秒脉冲作抽运光,采用单光束Z-扫描技术对具有激发态分子内质子转移效应的有机分子2-(2′-羟基苯基)苯并噻唑(HBT)在其双光子吸收区的非线性光学特性进行了研究.实验结果表明,对532nm波长的光,HBT分子存在明显的双光子吸收.通过拟合开孔Z-扫描实验数据,求解了HBT分子在其双光子吸收区的非线性吸收系数,并探讨了抽运光强度对介质双光子吸收效应的影响.采用高斯分解法,通过拟合闭孔Z-扫描除以开孔Z-扫描数据,理论推导并计算了在介质对抽运光存在非线性吸收的情况下HBT分子的非线性折射率,以及不同入射光强度时HBT分子的三阶非线性极化率实部和虚部的值.计算结果表明,理论分析与实验结果较好地符合,这些结果为进一步研究和开发此类材料的应用提供了理论与实验依据.     

长程电子关联对聚合物中激子极化率的影响

本文研究了在外电场下高分子的线性极化率和三阶非线性极化率,发现电子电子相互作用使激子线性极化率和三阶非线性极化率都降低,而长程电子关联效应的作用更进一步降低 和。准确地计算高分子聚合物的极化率可以更好的理解共轭聚合物的长程电子关联对有机分子线性和非线性响应的影响,确定其结构与非线性光学性质的关系。     

长程电子关联对聚合物中激子极化率的影响

本文研究了在外电场下高分子的线性极化率和三阶非线性极化率,发现电子-电子相互作用使激子线性极化率χ(1)xx和三阶非线性极化率χ(3)xxxx都降低,而长程电子关联效应的作用更进一步降低χ(1)xx和χ(3)xxxx.准确地计算高分子聚合物的极化率可以更好的理解共轭聚合物的长程电子关联对有机分子线性和非线性响应的影响,确定其结构与非线性光学性质的关系.     

Second-order nonlinear optical susceptibility in chalcone-group crystalline molecular compounds

A study is reported of the second-order nonlinear optical susceptibility in polycrystalline molecular materials of the chalcone group made by second-harmonic generation at a wavelength of 1.06 μm. Some of the compounds studied exhibit a high nonlinear activity and are transparent in the blue region of the spectrum. The measured macroscopic nonlinear polarizability χ ² was compared with the calculated values of β, the second-order molecular polarizability tensor. The high nonlinear optical polarizability observed in some chalcone compounds is shown to be related to crystal symmetry type. Fiz. Tverd. Tela (St. Petersburg) 41, 2084–2087 (November 1999)     

Calculations of Nonlinear Refractive Index of Alkali Halides

Theoretical values of the nonlinear refractive index n₂ of 16 rock salt-structure alkali halides are presented. The approach employed is based on the Phillips–Van Vechten interpretation of the bond polarizability model. Our results show that in halides with the same cation a monotonic, strong increase in n₂ with the linear refractive index can be observed.     

有机大分子三阶非线性光学材料的研究进展

根据分子结构特征评述了各类有机大分子三阶非线性光学材料结构与性能的关系。概述了三阶非线性光学性能的计算。分析了材料分子设计原理和展望了应用前景。     

Inclusion of non-orthogonality on the valence bond charge-transfer model for nonlinear optical properties of push—pull molecules

In models based on valence bond theory for predicting nonlinear optical properties of push-pull molecules, the wave functions representing resonance structures are assumed to be orthogonal. We have extended the two-state valence bond charge-transfer model to include non-zero overlap integrals. The resulting model leads to analytic formulae for the polarizability and hyperpolarizabilities, which are related to the overlap and other molecular parameters. In particular we report, as a function of the overlap: (i) relatively weak dependence of the first-order polarizability; (ii) significant variations in both the magnitude and the shape of the response curves corresponding to the second- and third-order polarizabilities. This result may be of relevance in the context of optical switching effects induced by chemical changes (related to the overlap) rather than the more conventional field-induced effect.     

基于键极化加和模型及其实验修正方法的超拉曼微观极化率张量元微分的简化方案-C2v对称性

相干反斯托克斯拉曼光谱(CARS) 和相干反斯托克斯超拉曼光谱(CAHRS)等高阶非线性光谱技术已经应用在动力学过程、基因表达谱筛选、高分辨率光谱分析等诸多领域。但因其涉及到的高阶微观极化率张量元数量众多,对其光谱信号进行定量分析非常困难。文献通过理论分析将CARS和CAHRS的微观极化率张量元分解为拉曼微观极化率张量元微分α′_i′j′和超拉曼微观极化率张量元微分β′_i′j′k′的乘积,将高阶光谱定量分析的困难简化为对低阶光谱的分析。该研究处理了具有C_2v对称性分子基团,提出一种利用键极化加和模型及其实验修正的方法简化超拉曼微观极化率张量元微分β′_i′j′k′比值的方案。首先利用键极化加和模型方法,在对C_2v分子基团局域模式假设的基础上,进行单键的局域模式假设,通过对单键伸缩振动进行简正振动模式的分析,并与单键的偶极矩表达式进行比较,得到单键的超拉曼微观极化率张量元微分β′_i′j′k′。在单键β′_i′j′k′结果的基础上利用键极化加和模型,对C_2v分子基团进行对称性分析,将基团中两个单键伸缩振动的β′_i′j′k′耦合,得到C_2v分子基团对称振动和反对称振动两种简正振动模式的超拉曼微观极化率张量元微分β′_i′j′k′的表达式。在此基础上对C_2v分子基团对称振动和反对称振动的β′_i′j′k′表达式进行理论推导,结合对应振动模式下不同偏振组合的超拉曼退偏率ρ_HR-SS和ρ_HR-AS及HV偏振组合时实验测量的超拉曼光谱强度比,得到超拉曼实验修正的C_2v分子基团β′_i′j′k′之间的比值。再结合文献中拉曼实验修正的拉曼微观极化率张量元微分α′_i′j′之间的比值,即可得到C_2v分子基团CARS和CAHRS的微观极化率张量元之间的比例关系,为定量分析高阶非线性光谱信息提供理论基础。     

A model of pair interactions in the theory of optical properties of fractal clusters

In the context of a binary model, the optical properties of a cluster consisting of metal nanoparticles of different sizes are considered. It is shown that the occurrence of different sizes of particles leads to a doubling of the number of resonances in the polarizability of a pair, which entails fundamentally new inferences about the absorption spectrum, polarization properties, and nonlinear effects in real metal nanocomposites.     

The Optical Properties of (C59N)2

Using the extended Hubbard model and sum-over-state method, we have calculated the linear polarizability α and the third-order nonlinear polarizability γ for (C₅₉N)₂. We find that (C₅₉N)₂ has very big γ value (around esu), and its α and γ values are bigger than those of C₅₉N. In particular, when 1.2 eV≤3ω, (C₅₉N)₂ as much larger γ values than C₅₉N.     

Discrimination of resonant and nonresonant contributions to the nonlinear refraction spectroscopy of ion-doped solids

Nonlinear refraction spectroscopy measurements were performed in resonance with absorption lines in Nd3+ and Cr3+ doped crystals. The observed line shapes can be explained by the interference of resonant and nonresonant contributions to the nonlinear refractive index. These effects were fully discriminated using a pump and probe configuration, in which a dispersive line shape was observed on the top of a plateau that was attributed to the polarizability difference between excited and ground states (Deltaalpha). A theoretical model was used to obtain Deltaalpha from the experimental data, and the results are in agreement with several previous experiments. Slow and fast light propagation are also discussed.     

Quantum dot as spin filter and spin memory

We present the first measurement of the polarizability and the permanent dipole moment of isolated KC60 molecules by molecular beam deflection technique. We have obtained a value of 2506+/-250 A(3) for the polarizability at room temperature. The addition of a potassium atom enhances by more than a factor of 20 the polarizability of a pure C60 molecule. This very high polarizability and the lack of observed permanent dipole show that the apparent polarizability of KC60 is induced by the free skating of the potassium atom on the C60 surface, resulting in a statistical orientation of the dipole. The results are interpreted with a simple model similar to the Langevin theory for paramagnetic systems.     

Induced birefringence in aqueous bio-macromolecular solutions

On the basis of results of linear and nonlinear optics investigation in L-Glutathione and Bovine-Serum Albumine aqueous solutions, the Kerr constants, nonlinear polarizabilities, effective optical anisotropies, anisotropic factor, scattering coefficient and orientation function as well as polarizability and optical anisotropy were calculated.     

Rotational-vibrational polarizability operator for nonlinear X<Subscript>2</Subscript>Y molecules: Application to the calculation of the Raman spectrum of the H<Subscript>2</Subscript>O molecule

For nonlinear X₂Y molecules, an expression for the transformed polarizability operator is obtained with an accuracy of up to the second order of the theory of perturbation. This operator is applied to the calculation of the intensities of Raman lines of the H₂O molecule. The corrections to the polarizability of the molecule associated with the vibrational-rotational interaction are shown to considerably change the integral intensity of a pure rotational band. The dependence of the average polarizability of the molecule on the vibrational quantum number V ₂, describing deformation vibrations, is estimated.     

Effect of ionic polarizability on oxygen diffusion in δ-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> from atomistic simulation

The effect of polarizability of cation dopants on oxygen diffusion in δ-Bi₂O₃ is determined using molecular-dynamics simulation in which the polarizability of the ions is treated within the shell model. It is found that the magnitude of the oxygen polarizability has no affect on diffusion. However, the high cation polarizability, associated with the lone pair of electrons in Bi, is found to be the key to achieving sustained oxygen diffusion. Consistent with earlier experimental results, the oxygen diffusion path is found to be between oxygen equilibrium sites, which are displaced from the 8c oxygen sites of the fluorite lattice.     

高压类氢原子能量与极化率的另一种计算

 本文采用新的试探波函数，对于关闭在半径为r₀球壳内的类氢原子模型，计算了其能量和极化率随球壳半径r₀和相应压强的变化规律。同文献[1]的结果相比，有明显的改善。     

Modelling of the phase transitions sequence in KNbO3 and BaTiO3

Interatomic potentials are determined in the framework of the nonlinear oxygen polarizability model to describe the structural behavior of KNbO₃ and BaTiO₃ as a function of temperature. To this purpose, the adiabatic potential is evaluated for different ferroelectric distortions and the model potential parameters are improved by comparing with total energies from full-potential LMTO calculations. Phonon dispersion curves are computed to test if the model reproduces the pronounced two-dimensional character instabilities found by first-principles lattice dynamics using a linear response approach. Finally, the phase diagram for KNbO₃ is obtained through a constant-pressure molecular dynamics simulation.     

Models of environmental effects on anion polarizability

This paper deals with three different approaches to the representation of environmental effects on anion polarizability in cubic crystals of the stoichiometry MX, where M is an alkali metal and X is a halogen. Ab initio embedded cluster calculations of the variation in anion polarizability with pressure in a fixed crystal type are presented and compared with experiment. The results are then used in a scaled ab initio model used to predict further values for the pressure dependence of the in-crystal anion polarizability. This scaled model is compared with a fully empirical ‘universal’ model due to Batana et al. based on polarizability change with ionic radius [1997, Molec. Phys., 92, 1029]. The assumptions of the two models differ substantially and the central purpose of this paper is to contrast these differences and highlight their consequences for prediction. Although the empirical model typically overestimates the experimental pressure derivatives, and the ab initio calculations somewhat underestimate them, it is shown that the assumption of incompressible cations in the scaled ab initio-derived model has a firmer physical basis than the empirical picture in which all ions are compressible.     

On the phenomenological theory of the linear electrooptical effect in uniaxial crystals

The linear electrooptical effect in uniaxial crystals is considered with the aid of direct tensor methods. Covariant expressions for finding biradials and ray refractive indices are developed. A general expression is derived relating the nonlinear optical polarizability parameters and the electrooptical properties of a crystal. The results are applied to cuts of uniaxial ammonium dihydrogen phosphate (ADP), potassium dihydrogen phosphate (PDP), and quartz crystals often used for light modulation. The induced phase differences between the light waves propagating in such crystals are found for the field orientations considered.