The theoretical studies on the two-photon absorption properties of symmetric 1,4-bis{2-[4-（2- aryl） phenyl] vinyl }- 2,5-bisdialkoxyb enzenes

On the level of the time-dependent hybrid density functional theory, the one- and two-photon absorption properties of a series of symmetric 4-bis 2-[4-(2-ary12) phenyl]vinyl-2,5-bisdialkoxybenzenes are studied respectively utilizing the analytic response theory and the few-state model methods. The calculated results show that the planarity of the geometrical structure plays a great role in enhancing the linear and nonlinear optical abilities of the molecule. However the effect of the length of the chain linked to the π-centre on the optical property is very little. For the investigated compounds, the A–π–A type charge-transfer molecules display more superior one- and two-photon absorption characteristics than the D–π–D type ones. Furthermore, the two-photon absorption results by use of few-state model are generally consistent with those by analytic response theory, demonstrating the reliability of the few-state model for evaluating the two-photon absorption cross section. The numerical simulations are in good agreement in tendency with the available experimental measurements.     

一种新型双共轭链分子非线性光学性质的理论研究

对实验室合成的双共轭链分子1,4-二(4-二乙胺基苯乙烯基)-2-［4-(N-甲基-N-羟乙基)氨基-4′-硝基偶氮苯］-5-己烷氧基苯(BSBAB)及合成它的单共轭链分子的单光子和双光子吸收特性在从头计算的基础上利用密度泛函理论进行了研究.分子BSBAB的优化结构显示，组成该分子的横链和纵链除了保持各自的共轭面外，几近相互垂直.因此，分子BSBAB较好地继承了两个单共轭链分子的光学特性.计算结果表明，在低能量范围内，分子BSBAB具有三个双光子吸收峰，分别来自于两个单共轭链分子以及两者的耦合作用.从理论上证明了双共轭链分子BSBAB是一种具有宽带强双光子吸收的分子材料.理论结果和实验结果符合得较好.在HF水平上的响应函数方法进一步证实了有限态求和方法计算结果的可靠性.还给出了电荷转移态的电荷迁移过程. 关键词： 双光子吸收 双共轭链有机分子 非线性光学     

Characterization of the two-photon absorption resonance that is due to the internal charge-transfer transition of a push pull molecule, 4-(diethylamino)-beta-nitrostyrene

The two-photon absorption resonance that is due to the internal charge-transfer transition of an organic push-pull molecule has been characterized. A nonlinear absorption spectrum of the 4-(diethylamino)- beta-nitrostyrene molecule was measured in a tetrahydrofuran solution by optical Kerr ellipsometry. The shape and the amplitude of the two-photon absorption spectrum are well described by a model that uses the relevant one-photon absorption spectrum related to the internal charge-transfer transition.     

Solvent effects on optical properties of a newly synthesized two-photon polymerization initiator： BPYPA

Time-dependent hybrid density functional theory in combination with polarized continuum model is applied to study the solvent effects on the geometrical and electronic structures as well as one- and two-photon absorption processes, of a newly synthesized asymmetrical charge-transfer organic molecule bis-（4-bromo-phenyl）-[4-（2-pyridin-4-yl-vinyl）phenyl]-amine （BPYPA）. There exist two charge-transfer states for the compound in visible region. The two-photon absorption cross section calculated by a three-state model and solvatochromic shift of the charge-transfer states are found to be solvent-dependent, where a nonmonotonic behaviour with respect to the polarity of the solvents is observed. The numerical results show that the organic molecule exhibits a rather large two-photon absorption cross section as compared with the compound 4-trans-[p-（N, N-Di-n-butylamino）-p-stilbenyl vinyl] pyridine （DBASVP） reported previously, and is predicted to be a good two-photon polymerization initiator. The hydrogen-bond effect is analysed. The computational results are in good agreement with the measurements.     

以芘为中心系列衍生物的单光子和双光子吸收特性理论研究

在含时密度泛函理论的水平上,利用响应场理论方法研究了以芘为中心系列衍生物的单光子和双光子吸收特性. 研究结果表明,在低能量范围内,每个分子有多个电荷转移态. 单光子吸收性质与实验结果符合较好. 随着分子尺寸的增加,分子的最大双光子吸收截面显著增加,其中具有四分枝结构分子的最大双光子吸收截面是单枝结构分子的5.6倍. 同时,分子的双光子吸收截面与分子结构的对称性有关.其中对称结构分子具有较大的双光子吸收截面.     

二苯乙烯衍生物分子双光子吸收截面：官能团对称性的影响

选取了具有不同对称性的二苯乙烯系列衍生物分子，在HF水平上，利用响应函数方法，研究了该系列分子的单光子和双光子特性. 研究结果表明，该系列分子具有较强的双光子特性. 在可见光范围内，反对称分子的最大双光子吸收态是第一激发态，而对称分子的最大双光子吸收出现在第四激发态. 相对于对称分子而言，反对称分子具有更大的双光子吸收截面. 因此，分子的对称性是否比不对称性更有利于增大分子的双光子吸收截面，还与分子的π中心部分的特性有关. 还给出了电荷转移态的电荷迁移过程. 关键词： 双光子吸收 响应函数方法 非线性光学     

Resonant propagation of femtosecond laser pulse in DBASVP molecule：one-dimensional asymmetric organic molecule

We have investigated the resonant propagation of femtosecond laser pulse in 4-trans-[p-（N, N-Di-n-butylamino）- p-stilbenyl vinyl] pyridine medium with permanent dipole moments. The electronic structures and parameters for the compound have been calculated by using density functional theory. In the optical regime, there is one charge-transfer state, and the molecule can thus be simplified as a two-level system. Both the one- and two-photon transitions occur between the ground and charge-transfer states. The numerical results show that the permanent dipole moments have an obvious effect on the propagation of the ultrashort pulse laser. The ideal self-induced transparency disappears for 2π pulse, and second harmonic spectral components occur significantly due to the two-photon absorption process. For the 6π pulse, continuum frequency generation is produced and a shorter duration pulse in time domain with 465 as is obtained.     

Two-photon absorption properties of aggregation systems on the basis of (E)-4-(2-nitrovinyl) benzenamine molecules

Aggregation effect caused by the intermolecular hydrogen-bonding interactions on two-photon absorption properties of (E)-4-(2-nitrovinyl) benzenamine molecules is studied at a hybrid density functional level. The geometry optimization studies indicate that there exist two probable conformations for the dimers and three for the trimers. A strong red-shift of the charge-transfer states is shown. The two-photon absorption cross sections of the molecule for certain conformations are greatly enhanced by the aggregation effect, from which a ratio of 1.0:2.6:3.6 is found for the molecule and its dimer and trimer with nearly planar structures. Namely, a 30 or 20 percent increase of the two-photon absorption cross section is observed.     

超短脉冲激光在DBASVP分子中传播时的双光子面积演化和光限幅效应

以一维不对称π共轭分子体系（DBASVP分子）为介质,在双光子共振条件下,从双光子面积定理和严格数值求解Maxwell-Bloch方程两方面出发,分别研究超短脉冲激光在该有机分子介质中的传播过程,从而探讨双光子面积的演化规律,并分析双光子面积定理的适用性.提出了一种数值模拟分子介质光限幅特性的理论方法.分子的电子结构和电偶极矩是基于密度泛函理论利用从头计算方法得到的.研究结果表明,基于慢变幅和慢变相近似以及单模场条件下的双光子面积定理不能很好地描述超短脉冲的双光子面积在该分子介质中的演化规律.基于双光子吸收的分子光限幅特性与分子介质的厚度有关. 关键词： 双光子吸收 光限幅效应 双光子面积定理 超短脉冲激光     

双光子吸收的Franz-Keldysh效应

从实验上证实Hg_0.695Cd_0.305Te 光电二极管空间电荷区中存在双光子吸收的Franz-Keldysh效应.利用一个皮秒Nd:YAG激光器抽运的光学参量产生器和差频产生器作为激发光源,测量了入射波长为λ₀=7.92μm的脉冲激光所激发的光响应随入射光强的变化关系.脉冲光响应峰值强度随入射光强的增大呈现二次幂函数增强趋势.采用等效RC电路模型将脉冲光伏信号峰值与入射光强相关联,得到空间电荷区中强电场下单光束 关键词： Franz-Keldysh效应 碲镉汞 双光子吸收 脉冲光伏信号     

以二乙烯硫/砜基为中心的新型电荷转移分子双光子吸收特性

理论研究分子结构与双光子吸收性质之间的关系对于指导实验者设计与合成功能分子材料具有重要意义. 在杂化密度泛函水平上, 利用响应函数方法, 计算了一类以二乙烯硫/砜基为中心的新型电荷转移分子的双光子吸收截面, 并在相同计算水平上, 与联苯乙烯类强双光子吸收分子做了比较; 以新型电荷转移分子为基础, 利用异构效应, 设计出了可以增强双光子吸收强度的分子结构. 研究表明, 在可应用波长范围内, 该系列分子表现出较强的双光子吸收响应, 与相似共轭长度的强双光子吸收分子具有相同量级的双光子吸收截面; 二乙烯硫/砜基在分子中心作为吸电子基团可以形成有效的电荷转移分子; 改变咔唑基的连接方式可以有效提高双光子吸收截面. 该研究为实验合成新型双光子吸收分子材料提供了理论依据.     

硅的间接跃迁双光子吸收系数谱

利用皮秒Nd:YAG脉冲激光器作为激发光源,测量出光子能量介于1.36 μm (0.912 eV)—1.80 μm (0.689 eV)之间的硅间接跃迁双光子吸收系数谱.尽管此波段范围内的激光光子能量小于硅间接带隙,但当激光辐照在硅基光电二极管受光面时,在二极管两电极端仍然探测到了显著的脉冲光伏信号.光伏信号峰值强度与入射光强呈二次幂函数关系,表明其是双光子吸收过程.采用pn结等效结电容充放电模型,将光伏响应信号峰值与入射光强相关联,从中提取出硅的间接跃迁双光子吸收系数,改变入射波长得到系数谱.研究表明:     

反-4,4''-双(N,N-二丁胺基)二苯乙烯分子双光子吸收性质研究

对于实验室合成的反-4,4'-双(N,N-二丁胺基)二苯乙烯分子,实验测量了该分子的单光子和双光子荧光谱,然后从理论上研究了其单光子和双光子吸收特性.研究结果表明,在低能量范围内,分子的单光子吸收主要发生在分子的第一激发态,而分子的双光子吸收主要发生在分子的第二和第四激发态上.该分子在相应系列衍生物中具有最大的双光子吸收截面.分子的相关能对分子的激发态能量影响较大.我们给出了分子基态与电荷转移态的电荷转移过程,并从理论上定性解释了双光子聚合反应的聚合机理.     

Nonlinear optical parameters and optical limitation in cobalt-doped polyvinylpyrrolidone solutions

Nonlinear optical parameters (nonlinear refractive indices and nonlinear absorption coefficients) of solutions of polyvinylpyrrolidone doped by cobalt to various concentrations are measured at the lasing and second-harmonic wavelengths of a picosecond Nd:YAG laser (λ=1064 and 532 nm, respectively, and τ=35 ps). Data on optical limitation in these solutions are presented. The absence of nonlinear absorption in the IR spectral range and its significant effect in the visible range are demonstrated. Optical limitation at a wavelength of 1064 nm is related to defocusing, whereas at 532 nm, this effect is caused by two-photon absorption and partially by inverse saturated absorption and defocusing. Nonlinear optical parameters of metal-polymer complexes are reported.     

The effect of bromine substitution on the charge-transfer emission of the complex of phenanthrene and tetracyanobenzene

The absorption spectra of the charge-transfer complexes of sym-tetracyanobenzene (TCNB) with phenanthrene, 9-bromophenanthrene, and 9,10-dibromophenanthrene are measured in chloroform solutions at room temperature. The total emission and phosphorescence spectra of the donors and the complexes are measured at 77 K in rigid glasses. The phosphorescence decay lifetimes are determined for phenanthrene, TCNB, and for the phenanthrene-TCNB complex, and a decrease in the phenanthrene-TCNB complex lifetime relative to the lifetimes of the two components is observed. The luminescence spectra of the complexes exhibit both a red shift and a lack of structure as compared with the donor spectra. The results are interpreted, in agreement with the results of Iwata et al. for the phenanthrene-TCNB complex (1), as an indication that there is a considerable degree of charge-transfer character in the lowest triplet state (T₁). Bromine substitution leads to a decrease in the energy of the phenanthrene triplet state. As a result, the energy gap between the donor molecule triplet state and the complex charge-transfer triplet state decreases from phenanthrene, to 9-bromophenanthrene, to 9,10-dibromophenanthrene. The results suggest that the proximity of these two triplet states in 9,10-dibromophenanthrene and its charge-transfer complex leads to some local donor triplet state character in the emitting complex triplet state.     

Theory of two-photon photothermal deflection spectroscopy in stationary and flowing media for arbitrary optical pulse length

A general theory of pulsed two-photon photothermal deflection spectroscopy (PTDS) is presented. We find that there are significant enough differences in the amplitude and temporal evolution of PTDS signals between the results of the single- and two-photon theories that if one tries to interpret two-photon data with single-photon theory, the extracted values may be considerably in error. Our theory is sufficiently general that it incorporates both stationary and flowing media and considers optical pulses of arbitrary length. Moreover, the temporal profile of the optical pulse is explicitly taken into account. The two-photon absorption coefficient is explicitly expressed in terms of oscillator strengths and Clebsch–Gordan coefficients, and the Doppler width for both co-propagating and counter-propagating beams is taken into account. Although the theory is primarily developed for atomic and molecular vapors, it can easily be adapted for condensed matter by expressing the absorption coefficient in terms of the properties of the liquid or solid under investigation. PACS 82.80.Kq; 42.62.Fi; 39.30.+w     

Flexible alteration of optical nonlinearities of iodine charge-transfer complexes in solutions

The type of donor used is found to influence greatly the optical nonlinearities of iodine charge-transfer (CT) complexes in solutions for several solvents. The magnitude and sign changes of nonlinear absorption of iodine CT complexes for different solvents as donors are observed, which implies the transition from saturable absorption to reverse saturable absorption. Compared with C60 in toluene, iodine CT complexes with toluene and benzene demonstrate larger reverse saturable absorption. Meanwhile, flexible alteration of optical nonlinearities is easily obtained by adjusting the mixture ratio of different solvents, yielding a prospective means of constructing a nonlinear medium with a large nonlinear coefficient.     

新型多共轭链有机分子双光子吸收特性的理论研究

在密度泛函理论水平上,利用解析响应函数方法研究了以（4-{2-［4-（2-吡啶-4-乙烯基）-苯基］-乙烯基}-苯基）-胺为基本结构单元的单支、双支和三支共轭链有机分子的单光子和双光子吸收特性.计算结果表明,这三种有机分子都具有较大的线性和非线性吸收强度.在紫外-可见光区域,它们的单光子吸收谱都存在两个峰,这与实验结果符合较好.在近红外区域,多共轭链有机分子呈现出宽达300 nm的宽带双光子吸收,单支、双支和三支分子的最大双光子吸收截面比约为1.0∶2.3∶4.0,其中三支分子具有最大的双光子吸收截面101.73×10^-48 cm⁴·s.从理论上进一步证实,增加分子的共轭链可有效提高分子的双光子吸收特性.同时还给出了电荷转移态的电荷迁移过程. 关键词： 双光子吸收 响应函数方法 多共轭链有机分子     

双光子光学多稳态理论

本文系统地研究了双光子共振作用的光学多稳态理论。在平均场近似下求出的状态方程包含了动态斯塔克效应及弛豫时间参数。指出了在平均场近似下,F-P腔与单向环形腔的状态方程有基本相同的形式。分析了双光子光学多稳态的两种物理机构——克尔效应与饱和吸收效应。在一定条件下这两种效应的共同作用可导致双稳态、双双稳态及三稳态。进一步还给出了区分双稳态、双双稳态及三稳态的判别式。最后还研究了双光子四波混频位相复共轭反射率的双稳态及多稳态。 关键词：