染料J聚集体Langmuir-Blodgett膜光致发光谱的温度影响与多声子跃迁

在20—300K的范围内测量了三种花青染料聚集体Langmiur-Blodgett(LB)膜的光致发光谱。随着温度下降零声子线J峰强度的增大,观察到声子伴带的异常加强。分析表明生长不均匀的聚集体B膜具有低维晶体的特性,声子耦合强,且无辐射跃迁起着重要的作用。     

染料J聚集体Langmuir-Blodgett膜光致发光谱的温度影响与多声子跃迁

在20—300K的范围内测量了三种花青染料聚集体Langmiur-Blodgett(LB)膜的光致发光谱。随着温度下降零声子线J峰强度的增大,观察到声子伴带的异常加强。分析表明生长不均匀的聚集体B膜具有低维晶体的特性,声子耦合强,且无辐射跃迁起着重要的作用。     

LB薄膜中四新戊氧基酞菁锌和四壬基酞菁铜分子聚集体的吸收光谱的温度特性

本文制备了四新戊氧基酞菁锌(Tetra-neopentoxy phthalocyanine zine)(TNPPeZn)和四壬基酞菁铜(Tetra-nonyl phthalocyanine copper)(TNPeCu)两种酞菁衍生物的Langmuir-Blodgett(LB)薄膜.通过测量10～473K温度下的吸收光谱,研究了两种薄膜的分子聚集状态.TNPPeZn的LB薄膜中,存在着分子单体和分子二聚体,在吸收光谱中分别表现为680nm和620nm的吸收峰.随着温度的升高,分子单体逐渐转变为分子二聚体,这个过程是不可逆的.TNPeCu的LB薄膜中,除了分子单体和分子二聚体以外,还有吸收为740nm的分子J聚集体存在.随着温度的变化,J聚集体发生可逆变化.     

LB膜的制膜条件优化及其对光学性能的影响

通过紫外-可见吸收光谱、二次谐波振荡和稳态荧光的测量,研究了半花菁(DAEP)Langmuir-Blodgett(LB)膜在不同制膜条件(压膜速度、半花菁和花生酸混合、亚相中加入碘离子)下,LB膜样品中半花菁分子的聚集体性质的改变和对非线性光学性能的影响.实验发现,纯半花菁LB膜中分子形成H-聚集体,从而导致吸收峰、荧光峰的蓝移和分子二阶非线性极化率β的减少.分子聚集程度的减少和分子二阶非线性系数β的增加可以通过增大压膜速度、半花菁和花生酸混合、亚相中加入碘离子等方法实现.     

感绿菁染料J-聚集体吸附在氯化银微晶表面的吸收光谱

染料J-聚集体对于现代彩色信息记录与存储材料、生物光电子器件、光合作用、太阳能转换与存储等方面具有十分重要的应用前景和理论意义。感绿菁染料在适当浓度时,对立方体氯化银微晶有增感效应,文章应用吸收光谱法对增感后的氯化银微晶样品进行了研究。研究表明, 增感染料浓度低于0.02 mL(染料浓度为5.0 mg·mL-1)/40 g乳剂时,感绿菁染料在立方体氯化银表面不形成J-聚集体,吸收光谱没有J-聚集体吸收峰出现;当染料浓度高于0.2 mL(染料浓度为5.0 mg·mL-1)/40 g乳剂时,染料开始在立方体氯化银微晶表面聚集并形成J-聚集体,吸收光谱有J-聚集体吸收峰出现。随染料浓度进一步增加,J-聚集体的吸收明显加强,吸收峰有微小的红移。     

取代基对双酞菁铥LB膜及光谱特性的影响

采用紫外-可见吸收光谱的方法研究了三种稀土夹心双酞菁铥化合物在溶液和LB膜中的聚集性和光谱特性。实验结果表明三种稀土双酞菁化合物在氯仿溶液中形成了H-聚集体,但当浓度比较低时,溶液中表现出单体的吸收。取代基OC₈H₁₇的加入使氯仿溶液中双酞菁铥化合物的聚集性减弱,而且使得吸收峰发生红移,对吸收峰的强度也有较大的影响,造成了Soret吸收带的分裂。另外,取代基OC₈H₁₇对LB膜中双酞菁分子的存在状态有较大的影响,在LB膜中,TmPc₂和TmPcPc*分子以H-聚集体的形式存在,而TmPc*₂分子以T-聚集体的形式存在。形成LB膜后,由于双酞菁分子之间排列紧密,相互作用加强,使得薄膜中分子聚集体的吸收峰相对于溶液中聚集体的吸收峰发生了一定的红移,薄膜中分子排列方向的不同对吸收光谱也有一定的影响。     

染料J聚集体Langmuir_Blodgett膜光致发光谱的温度影响与多声子跃迁

在2 0 一3 0 0 K 的范围内测量了三种花青染料聚集体L a n g m i u r 一B lo d g e t t (L B ) 膜的光致发光谱. 随着温度下降零声子线J 峰强度的增大, 观察到声子伴带的异常加强. 分析表明生长不均匀的聚集体L B 膜具有低维晶体的特性, 声子祸合强, 且无辐射跃迁起着重要的作用. 关键词：     

温度对稀土夹心双萘酞菁LB膜光学性质的影响

 采用线性吸收谱和二次谐波产生技术研究了温度对具有中心对称结构的稀土夹心双萘酞菁化合物LB膜光学特性及其LB膜结构的影响。研究发现，加热可以使其LB膜的结构及分子间的相互作用发生变化，并形成J聚集体，从而使得吸收峰发生红移。稀土夹心双萘酞菁化合物约在40 ℃时其二次谐波信号有一个极小值，约在65 ℃时该化合物发生相变，使得二次谐波信号产生极大值，二次谐波信号最小时温度可高达180 ℃，说明该化合物的化学结构较为稳定。     

表面增强能量转移效应的研究

通过分析2、2′菁染料水溶液、银胶体以及2、2′菁染料吸附于银胶表面时的吸收光谱得知,2、2′菁染料吸附于银胶表面时,有J聚集体出现,通过分析基频及高阶线性Raman光谱,证实了一些低波数的Raman信号是由J聚集体产生的,从而进一步证实了吸附于银胶表面的2、2′菁染料以单体和J聚集体形式共存.同时,由吸收光谱还可以看出,2、2′菁染料分子及其J聚集体分子的吸收带都处于银胶吸收带的半高宽范围内,满足共振条件,当用不同激发波长(514.5 nm和488 nm)的光激发吸附于银胶表面的2、2′菁染料时,观察到了J聚集体的敏化荧光,而用此激发光激发2、2′菁染料水溶液时,就没有观察到J聚集体的敏化荧光,从而说明了银胶表面的存在,加速了单体2、2′菁染料分子与其J聚集体分子之间的能量转移速率.     

4-硝基-4′-氨基偶氮苯的光学性质研究

采用紫外可见吸收和二次谐波产生技术研究了“推-拉”型偶氮苯分子Langmuir-Blodgett(LB)膜的光谱和二阶非线性光学特性.4-硝基-4′-氨基偶氮苯(NAA)分子能制成很好的LB多层膜,在稀溶液中以单体的反式异构体形式存在,在膜中主要以J-聚集体的形式存在,LB膜的紫外可见吸收谱的吸收峰较之溶液的发生了52 nm的红移.NAALB膜的二阶非线性极化率χ(2)为19.59×10－8 esu,一阶超极化率β值较大,约为1.974×10－29 esu.其光学二阶非线性起源于电偶极子机制.     

The molecular aggregation of pyronin Y in natural bentonite clay suspension

The molecular aggregation and spectroscopic properties of Pyronin Y (PyY) in the suspension containing natural bentonite clay were studied using molecular absorption, steady-state and time-resolved fluorescence spectroscopy techniques. Interaction between the clay particles and the cationic dye compounds in aqueous solution resulted in significant changes in spectral properties of PyY compared to its molecular behavior in deionized water at the same concentration. These changes were due to the formation of dimer and aggregate of PyY in the clay suspension as well as the presence of the dye monomer. The H-type aggregates of PyY in the clay suspension were identified by the observation of a blue-shifted absorption band of the dye compared to that of its monomer. In spite of diluted dye concentrations, the H-aggregate of PyY in the clay suspension was formed. The intensive aggregation in the clay suspension attributed to the localized high dye concentration on the negatively charged clay surfaces. Adsorption sites of PyY on the clay particles were discussed by deconvulated absorption and excitation spectra. Fluorescence spectroscopy studies revealed that the fluorescence intensity of PyY in the clay suspension is decreased by H-aggregates drastically. Moreover, the presence of H-aggregates in the clay suspension resulted in the decrease of fluorescence lifetime and quantum yield of PyY compared to those in deionized water.     

八丁氧基-2,3-萘酞菁铜(Ⅱ)的合成与UV光谱研究

采用分子碎片法合成了5,9,14,18,23,27,32,36-八丁氧基-2,3-萘酞菁铜,利用元素分析、红外及紫外可见光谱进行了表征。配合物的电子吸收光谱表明:新配制的氯仿溶液中萘酞菁铜的Q带H聚集体和单体的吸收峰在758、854nm处,5h后单体和H聚集体的吸收峰基本消失,出现了798和909nm的错位H/J聚集体以及960nm的J聚集体吸收,12h后主要以795nm的H聚集体形式存在。     

Effect of surfactants on the aggregation of pyronin B and pyronin Y in aqueous solution

Molecular dynamics of pyronin B (PyB) and pyronin Y (PyY) in aqueous solution containing different surfactants were investigated by using absorption and fluorescence spectroscopy techniques. First, the interactions of PyB and PyY with the negatively charged surfactant sodium dodecyl sulphate (SDS) were investigated in the below and above critical micelle concentration (cmc). The H-aggregate formation of the dye compounds was observed for below the cmc of SDS surfactant. The absorbance of H-aggregate absorption band of PyB and PyY decreased according to the aggregate-monomer equilibrium by increasing SDS surfactant concentration towards the cmc. Therefore, equilibrium constants of the aggregate formation and oscillator strengths of monomer and aggregate of the dye compounds were calculated from spectral studies. Moreover, aggregate formation dynamics was discussed in terms of thermodynamic functions by using temperature studies. The interactions of PyB and PyY with the positively charged hexadecyltrimethylammonium bromide (CTAB) and neutral Triton X-100 (TX-100) were also studied and it was observed that there was no aggregate formation on the absorption and fluorescence spectra for below and above the cmc.     

Strong coupling in a microcavity LED

Thin films of polyelectrolyte/J aggregate dye bilayers with high absorption coefficient (6 nm thick with alpha approximately equal to 1.0 x 10(6) cm(-1)) inserted in an optical microcavity enable the cavity quantum electrodynamic strong coupling limit to be reached at room temperature with a coupling strength (Rabi splitting) of 265 +/- 15 meV. By embedding these films in a resonant cavity organic LED structure, we demonstrate the first emissive electrically pumped exciton-polariton device.     

Effect of aggregation on the absorption cross-section of fractal soot aggregates and its impact on LII modelling

This study concerns the effect of particle aggregation on laser heating rate of soot aggregates in laser-induced incandescence. Three aggregate absorption models were investigated: the Rayleigh-Debye-Gans approximation, the electrostatics approximation, and the numerically exact generalized multi-sphere Mie-solution method. Fractal aggregates containing 5-893 primary particles of 30 nm in diameter were generated numerically using a combined particle-cluster and cluster-cluster aggregation algorithm with specific fractal parameters typical of soot. The primary particle size parameters considered are 0.089, 0.177, and 0.354. The Rayleigh-Debye-Gans approximation neglects the effect of particle aggregation on absorption; so it underestimates the aggregate absorption cross-section area by approximately 10%, depending on the aggregate size and primary particle size parameter. The electrostatics approximation is somewhat better than the Rayleigh-Debye-Gans approximation, but cannot account for the effect of primary particle size parameter. The aggregate absorption submodel affects the calculated soot temperature in laser-induced incandescence mainly in the low laser fluence regime. At high laser fluences, the effect diminishes due to the enhanced importance of soot sublimation cooling and neglect of aggregation effect in the sublimation in the present numerical model of laser-induced incandescence.     

The effect of particle aggregation on the absorption and emission properties of mono- and polydisperse soot aggregates

This study concerns the effect of soot-particle aggregation on the soot temperature derived from the signal ratio in two-color laser-induced incandescence measurements. The emissivity of aggregated fractal soot particles was calculated using both the commonly used Rayleigh–Debye–Gans fractal-aggregate theory and the generalized Mie-solution method in conjunction with numerically generated fractal aggregates of specified fractal parameters typical of flame-generated soot. The effect of aggregation on soot temperature was first evaluated for monodisperse aggregates of different sizes and for a lognormally distributed aggregate ensemble at given signal ratios between the two wavelengths. Numerical calculations were also conducted to account for the effect of aggregation on both laser heating and thermal emission at the two wavelengths for determining the effective soot temperature of polydisperse soot aggregates. The results show that the effect of aggregation on laser energy absorption is important at low fluences. The effect of aggregation on soot emissivity is relatively unimportant in LII applications to typical laminar diffusion flames at atmospheric pressure, but it can become more important in flames at high pressures due to larger primary particles and wider aggregate distributions associated with enhanced soot loading.     

三氮吲哚嗪对增感染料吸收光谱和荧光谱的影响

本文研究了三氮吲哚嗪（ＴＡＩ）对三种卤化银乳剂增感染料水溶液的吸收光谱和荧光光谱的影响。研究表明ＴＡＩ能使这些染料的各吸收峰强度增强，对容易形成Ｊ聚集体的染料来说，更有利于其Ｊ态光谱吸收；当三氮吲哚嗪的浓度达到一定值后，它能使染料Ｈ聚集体分解成单分子，利于单分子光谱吸收；结果说明染料的荧光发射也随溶液中ＴＡＩ浓度的增大而增强。本文还讨论了产生这种现象的原因。     

Intrinsic absorption threshold of stishovite and coesite

The optical absorption spectra of the small mono-crystals samples of stishovite and coesite were studied at first. The intrinsic absorption threshold of stishovite is determined at 8.75 eV, being probably, highest in the family of different crystalline polymorph modifications of silicon dioxide. The absorption spectrum of stishovite is independent of temperature (studied in the range 290-450 K). The intrinsic absorption threshold of coesite mono-crystal situated near 8.6 eV at 293 K, coincides within experimental errors with that of α-quartz crystal, and depends on temperature, as used to be for the tetrahedron structured silicon dioxide crystalline modifications. A broad absorption band with a first spread maximum near 7.6 eV sides with intrinsic absorption threshold was found in the stishovite mono-crystal sample. Its low intensity (about 10 cm⁻¹) in an as-received sample shows on a defective nature of this band. No analogous band was detected in the sample of coesite.     

Influence of complex component and particle polydispersity on radiative properties of soot aggregate in atmosphere

The effects of morphological structure, water coating, dust mixing and primary particle size distribution on the radiative properties of soot fractal aggregates in atmosphere are investigated using T-matrix method. These fractal aggregates are numerically generated using a combination of the particle-cluster and cluster-cluster aggregation algorithms with fractal parameters representing soot aggregate in atmosphere. The radiative properties of compact aggregate notably deviate from that of the branched one, and the effect of morphology changes on the radiative properties in wet air cannot be neglected. However it is reasonable to use realization-averaged radiative properties to represent that of the aggregates with certain morphology. In wet air, the scattering, absorption and extinction cross-section and symmetry parameter of soot aggregates coated with water notably increase with water shell thickness. The mixing structures of dust have little effect on radiative properties of aggregates, but the volume fraction of dust has an obvious effect on extinction, scattering and absorption cross-section of aggregates when the size parameters are above the Rayleigh limit. Although the primary particle size distribution of soot aggregate has mild effect on the scattering albedo and asymmetry parameter, the deviations of the extinction, scattering, absorption cross-section among the three size distributions are significant in this study. The size distribution has a significant effect on forward scattering of phase function, while the effect can be neglected as the size parameter approaches to the Rayleigh limit.     

Efficiency of laser initiation and absorption spectra of PETN

A comparative study of the efficiency of the laser initiation of PETN by the first and second harmonics (1060 and 530 nm) of a neodymium-doped phosphate glass laser was performed. A significant difference in the efficiency of PETN initiation by the different harmonics was revealed: as the initial temperature of the sample increased from 373 to 450 K, the threshold initiation fluence decreased from 3.0 to 0.5 J/cm²; at the same time, the second harmonic failed to initiate PETN even at a fluence of 10 J/cm². The absorption spectrum of PETN was found to have a weak absorption band with a maximum at λ _m = 1020 nm. It was assumed that the high efficiency of initiation by the first harmonic is associated with light absorption (photo-initiation) by this band