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.     

不同溶剂中硝基苯胺分子非线性光学性质的研究

在含时密度泛函理论水平上研究了溶剂对硝基苯胺分子非线性光学性质的影响 .溶剂效应通过极化连续模型来研究 .首先采用极化连续模型在密度泛函理论水平上优化了硝基苯胺分子在溶剂中的几何结构 ,从而研究了溶剂引起硝基苯胺分子几何结构的变化 .然后采用极化连续模型在含时密度泛函理论水平上计算了不同溶剂中硝基苯胺分子的激发态能量和电偶极矩 ,并利用两态模型首次给出了不同溶剂中二次谐波振荡过程的一阶非线性超极化率的色散关系 .计算结果表明 ,极性溶剂对硝基苯胺分子的非线性光学性质有较大的影响 .在低的辐射场频率下 ,理论给出的一阶非线性超极化率的色散关系和实验结果符合得较好 .最后对所得结果从理论上给出了可能的解释并讨论了两态模型的可靠性 .     

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。     

分子动力学模拟方法在非线性光学中的应用

有机分子非线性光学材料在频率转换、电光调制和双光子吸收等方面具有重要的应用.介绍了近年来分子动力学模拟方法在有机分子非线性光学性质理论研究中的主要应用,包括电场极化效应、局域场因子、非线性极化率和双光子吸收等.此外,结合最新的科研工作,介绍了分子动力学模拟方法在溶剂效应和聚集效应研究中发挥的重要作用. 关键词： 分子动力学模拟 溶剂效应 聚集效应 双光子吸收     

乙二醇分子间氢键结构与溶剂效应

采用密度泛函理论在B3LYP/6-311++G~(**)水平上研究乙二醇在气相中分别与乙腈、丙酮、四氢呋喃、水、乙二醇形成氢键二聚体的结构性质,根据PCM(polarized continuum model)极化统一场模型讨论氢键溶剂效应.结果表明,五种氢键二聚体分子中的氢键属于红移氢键,溶剂使氢键二聚体分子的偶极矩变大,并对OH振动频率的影响不大.     

4-羟基-3-甲氧基肉桂酸的二阶非线性光学性质研究

分析了4羟基3甲氧基肉桂酸的分子结构特点,研究了其二阶非线性光学性质和固体样品的透光性能.结果表明它具有很强的二次谐波产生和较宽的透光波段,截止吸收波长λ_cut-off=420nm;抗光伤实验表明,该化合物具有较高的抗光伤阈值.计算了其分子二阶非线性光学系数β,并与相应的衍生物作了比较研究. 关键词： 4-羟基-3-甲氧基肉桂酸 二阶非线性光学性质 透光性能     

Density Functional Theory Study of Infrared and Ultraviolet Spectra of Urea L-Malic Acid

用密度泛函理论研究了新型二阶非线性光学晶体-L苹果酸脲.采用一些密度泛函理论方法计算了分子结构,比较得出PBEPBE/6-31+G(d,p)是计算分子结构的一种最佳的方法,然后给出了其红外和紫外可见光谱,并与实验结果作了比较,还结合分子轨道布局分析了紫外可见光谱. 同时结合极化连续模型利用密度泛函理论方法研究了L苹果酸脲在水中的几何结构及红外和紫外可见光谱,并指出了溶剂化效应对其性质的影响.     

对称型二烷氨基蒽醌的三阶非线性光学性质研究

研究了对称型二烷氨基蒽醌的三阶非线性光学性质。通过三维简并四波混频实验对１１种低浓度溶液样品的测试，其三阶非线性极化率｜χ（３）｜达１．８～３．４×１０－１３ｅｓｕ，分子的三阶非线性超极化率γ达１．９～３．５×１０－３１ｅｓｕ。讨论了分子结构对三阶非线性光学性质的影响。     

分子偶极聚合物驻极体的红外和可见光谱研究

本文利用红外和可见吸收光谱研究了具有二阶非线性光学活性的分子偶极聚合物驻极体材料中偶极子的取向稳定性与分子结构之间的关系，讨论了制备时所用的溶剂对材料微结构的影响。结果表明该材料在玻璃态温度下极化时，引起生色团分子偶极矩沿电场方向取抽，是建立在生色团分子共轭л体系被破坏的基础上，这是一种亚稳态。偶氮类分子的顺-反结构在光、热的作用下极易发生转变，是引起常温下生色团分子有序取向结构松驰的主要原因。制备时所用的溶剂将影响生色团分子在聚合物基底中的存在形式，进而影响分子偶极聚合物驻极体的稳定性。     

三-α-(2,4-二甲基-3-戊氧基)溴硼亚酞菁的三阶非线性光学性质研究

应用Z扫描技术，在波长为532nm、脉宽为8ns条件下，对一种新型亚酞菁配合物三-α-(2,4-二甲基-3-戊氧基)溴硼亚酞菁的三阶非线性光学特性进行了研究，结果发现，该新化合物有较强的反饱和吸收(β=3.7×10^-10 m/W)效应和非线性自聚焦折射效应(n₂=7.2×10^-11esu)，其三阶非线性极化率χ⁽³⁾=1.1×10^-11esu.分析了溴硼亚酞菁配合物特殊的锥形分子结构和重原子溴的轴向配位等因素对其三阶非线性光学性质的重要影响. 关键词： 亚酞菁 Z扫描 三阶光学非线性     

Dielectric relaxation study of aqueous 2-ethoxyethanol using time domain reflectometry technique

The complex permittivity spectra of 2-ethoxyethanol in water solutions have been studied at different concentrations and temperatures using a picosecond time domain reflectometry technique. The complex dielectric permittivity spectrum of 2-ethoxyethanol shows Cole-Davidson type behavior. Increase in dielectric relaxation time may be due to increase in hetero molecular interaction strength. Minimum in Excess dielectric constant values provides the information about stable complex adduct. The Kirkwood correlation factor, thermodynamic properties and Bruggeman factor have also been determined and the results are interpreted in terms of hydrogen bonding and interactions among the solute — solvent molecules.     

激发态分子内质子转移分子2-羟基-1-萘甲醛半碳酰腙的光谱特性

通过考察2-羟基-1-萘甲醛半碳酰腙(HNLSC)在不同极性溶剂中的吸收光谱和荧光光谱,详细研究了HNLSC分子在不同溶剂及酸、碱条件下的不同构型,证实了HNLSC具有典型的ESIPT特性。在非极性溶剂中分子主要以分子内氢键的闭式构型存在,这种闭式构型使分子具有ESIPT特性,在环己烷溶剂和高酸度极性溶剂中分子均表现出～415nm的正常荧光和～435nm处的反常ESIPT荧光。在极性质子溶剂中,因溶质和溶剂之间形成了分子间的氢键以及进一步去质子化,HNLSC形成了基态的溶剂化开式构型和离子构型,在吸收光谱中表现出～395nm的离子构型特征吸收。开式构型和离子构型阻断了分子内质子转移途径,因而在荧光光谱中仅表现出一个特征峰。实验进一步通过三乙胺和稀硫酸调节溶液体系的极性和酸度环境,证明在不同溶剂极性和酸度环境下,HNLSC分子不仅存在萘环上羟基变化引起的多种互变异构体间的转化平衡,同时存在—CHN—NH—CO—NH2结构域的烯醇式和酮式结构的相互转化。     

Distinctive thermodynamic properties of solute–solvent hydrogen bonds in self‐associated solvents

Solute–solvent hydrogen bonding affects reactivity and other properties of dissolved species. In self‐associated media, because of cooperativity and solvent reorganization, the thermodynamic functions of solute bonding with bulk solvent can be different from those of bimolecular solute–solvent complexes. Using available experimental data on the Gibbs free energies of solvation in aliphatic alcohols and water, we have determined the energies of solute–solvent hydrogen bonding for various proton accepting solutes. We show that the increase in the strength of hydrogen bonds because of the cooperative effect is strong for bonding with bulk water and significantly less so with bulk aliphatic alcohols. The hydrogen bonding Gibbs free energies for the same solute with bulk water and alcohol are correlated, but they correlate poorly with the energies of formation of the corresponding bimolecular solute–solvent complexes. Thus, the traditional hydrogen bond basicity scales, based on data for bimolecular complexes, do not correctly describe the thermodynamics of hydrogen bonding with self‐associated solvents. Our results may help to define a separate solute basicity scale for associated media. Copyright © 2012 John Wiley & Sons, Ltd.     

Nonlinear optical properties of stilbene and azobenzene derivatives containing azaphosphane groups

We have studied the nonlinear optical (NLO) properties of some donor–acceptor molecules with stilbene and azobenzene molecules as backbone. We have used the nitro group as the acceptor and azaphosphane (R₃P=N–) as the donor group. To study the effect of variation of NLO properties, we have replaced the substituents (Rs) connected to the phosphorus atom by methyl, amine and phenyl groups. We find that both first-order polarizability and hyperpolarizabilities are larger for stilbene derivatives and is maximum for the phenyl substitution. Second-order polarizability is higher for methyl substitution. We have also obtained the two-photon absorption cross-section for these molecules. We find that both one-photon and two-photon absorption cross-sections are maximum for the same excited state (first excited state in the case of stilbene and second excited state in the case of azobenzene derivatives).     

Absorption, fluorescence studies and ab initio calculations on binary mixture of p-dimethylaminobenzaldehyde

Absorption as well as fluorescence emission studies of p-dimethylaminobenzaldehyde (DMABA) in solvents with different polarity have been reported by varying the concentration of the solute. Dual fluorescence corresponding to the non-polar (NP) and twisted intramolecular charge transfer (TICT) states has been observed. The optimized geometry of DMABA was evaluated using ab-initio theory at various levels. The optimized geometries of the hydrogen bonded complexes with the solvent molecules were also calculated with the theory Hartree Fock at the basis set 6-31+G (HF/6-31+G). The results have been used to understand the structure of the molecule and the spectral changes in terms of hydrogen bonding and solute–solvent interaction.     

Solvent dependent study of carbonyl vibrations of 3‐phenoxybenzaldehyde and 4‐ethoxybenzaldehyde by Raman spectroscopy and ab initio calculations

A Raman spectroscopy investigation of the carbonyl stretching vibrations of 3‐phenoxybenzaldehye (3Phbz) and 4‐ethoxybenzaldeheyde (4Etob) was carried out in binary mixtures with different polar and nonpolar solvents. The purpose of this study was twofold: firstly, to describe the interaction of the carbonyl groups of two solute molecules in terms of a splitting in the isotropic and anisotropic components and secondly, to analyze their spectroscopic signatures in a binary mixture. Changes in wavenumber position, variation in the anisotropic shift and full width half maximum were investigated for binary mixtures with different mole fractions of the reference systems. In binary mixtures, the observed increase in wavenumber with solvent concentration does not show linearity, indicating the significant role of molecular interactions on the occurrence of breaking of the self‐association of the solute. In all the solvents, a gradual decrease in the anisotropic shift reflects the progressive separation of the coupled oscillators with dilution. Γ_i(η_c), 3Phbz—solvent mixtures, exhibit a gradual decrease with decrease in the concentration of the solute which is an evidence on the influence of micro viscosity on linewidth. For 4Etob, the carbonyl stretching vibration shows two well‐resolved components in the Raman spectra, attributed to the presence of two distinct carbonyl groups: hydrogen‐bonded and free carbonyl groups. The intensity ratio of the carbonyl stretching vibration of these two types of carbonyl groups is studied to understand the dynamics of solute/solvent molecules owing to hydrogen bond interactions. Ab initio calculations were employed for predicting relevant molecular structures in the binary mixtures arising from intermolecular interactions, and are related to the experimental results. Copyright © 2009 John Wiley & Sons, Ltd.     

Interaction between solute molecules in medium density solvents

Solvation properties of solutes in supercritical, medium density solvents have been analysed using hypernetted-chain theory with the emphasis on the solvent-mediated interaction between solute molecules. The solvent and solute molecules are Lennard-Jones particles, and the solute is present at infinite dilution. Also a pair of solute molecules separated by different distances has been considered using reference interaction site model theory. Mainly, solvents at two typical densities (1.09_pc and 2.91_pc; pc is the critical density) that are in medium and high density regions, respectively, are treated. The temperature is set at 1.04T_C (T_c is the critical temperature). When the solute size is larger than the solvent size and the strength of the solute-solvent attractive interaction is greater than that of the solvent-solvent in the medium density region, the solvent structure confined between a pair of solute molecules is largely different from that near a single solute molecule. The confined solvent becomes denser and more stabilized as the distance between the solute molecules decreases, and an attractive interaction is induced between them. The interaction becomes even more attractive as the strength of the solute-solvent attractive interaction increases. The observations are qualitatively different from those in the high density region. Another high density region, which is well below the critical temperature, has been considered, but the behaviour observed is similar to that in the high density region above the critical temperature.     

Solvent effects on electronic absorption spectra of donor‐substituted 11,11,12,12‐tetracyano‐9, 10‐anthraquinodimethanes (TCAQs)

Solvent effects on the electronic absorption spectra of donor‐substituted 11,11,12,12‐tetracyano‐9, 10‐anthraquinodimethanes (TCAQs) 1 – 3 have been investigated in 32 well‐selected solvents. These compounds were chosen as model structures for charge‐transfer chromophores featuring second‐ and third‐order nonlinear optical properties. The resulting data were evaluated by means of theoretical models and (semi)empirical correlations determining the optical properties related to electron distribution and polarizability. We found that solvent effects on a polar D‐π‐A system do not depend on the donor/acceptor orientation (HOMO/LUMO localization) but especially on the length of the π‐system in between. The observed solvent effects are described with high accuracy by the applied theoretical models and linear combinations of physical quantities. Solvent polarization, permanent dipole moment, and molar volume substantially affect the longest‐wavelength absorption maxima. Solvent‐induced bathochromic shift resulting from the solvent polarity is described with high accuracy by the Born function. On the other hand, hypsochromic effects of the solvent permanent dipole moment are caused due to the slower reorganization of molecular dipoles compared with the rate of excitation. Solvent polarizability shifts the longest‐wavelength absorption maxima bathochromically with increasing length of the π‐conjugated system. Whereas this effect could be suitably described by the Onsager‐induced polarizability, the orientation polarizability was not found to be important. The solvent molar volume as a hypsochromic shift‐inducing factor is only relevant if the size of the solute and solvent molecules are comparable. If the size of the solute is considerably larger than that of the solvent molecules, the solvent behaves as a ‘shape continuum.’ Copyright © 2008 John Wiley & Sons, Ltd.     

Spectrophotometric Studies of the Influence of Organic Solvents and Substituents on Some Schiff Bases

The effect of the substituents, solvent polarities and hydrogen ion concentration on the electronic structure and UV/VIS absorption spectra of some Schiff bases, derivatives of N-(R-benzylidene)benzidine (R = o-NO₂ and o-OH, p-OH) and N-(R-furfurylidene)benzidine (R = H and 5 - NO₂), have been studied. The spectral shifts obtained in various organic solvents were discussed on the basis of the specific solute - solvent interactions through the formation of hydrogen bonds between hydrogen-bond donor (HBD) solvents and the benzidine nitrogen atom of the Schiff bases. Some interpretations of the electronic aspects of this type of hydrogen bonding were discussed as well as the stabilization effects due to the solvation. Finally, the pK values of the compounds were determined.