Evidence for the Cyclodextrin Mediated Aggregation of Cyanine Dyes into Oligomers

Based on the analysis of UV/Vis-and CD spectra of several cyanine dyes in - and -cyclodextrin a case is made for the aggregation of the dyes into oligomers. The criteria for this new type of aggregates are: (i) the appearance of a concentration and temperature dependent shoulder on the high energy side of the dimer band in the UV/Vis-spectra; (ii) two oppositely signed high intensity CD absorptions, one centered at the shoulder, the other at about the energy of the monomer absorption. Calculations based on coupled-oscillator theory support the contention that chiral dye aggregates are formed in the presence of cyclodextrins, most probably trimers and tetramers. From UV/Vis- and CD-data a helically twisted sandwich structure is suggested for these aggregates. In contrast to the reported inclusion complexes these aggregates must form — at least partly — outside the chiral host.     

Problems of the electronic structure of nonmetals in a wide energy region of fundamental absorption (review)

The article surveys the main unsolved problems of the electronic structure of nonmetals in a wide energy region of fundamental absorption. Udmurtia State University, 71, Krasnogeroiskaya Str., Izhevsk, 426034, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 3, pp. 299–315, May–June, 1999.     

Exciton reflection of ZnSe single crystals with account for the effect of the surface electric field

The mechanism of formation of an exciton reflection band is analyzed using a multilayer model of the near-surface region of ZnSe single crystals. It is shown that the appearance of a fine structure (a spike) in the reflection spectra at large damping parameters of the exciton is due to the surface electric field and the Stark exciton effect. The exciton-resonance energies and the damping parameters of free excitons for temperatures ranging from 12 to 100 K are determined by comparing experimental and predicted contours of the reflection spectrum. The surface concentration of charged centers and the characteristics of the space-charge region are evaluated within the framework of the model employed. Brest Polytechnic Institute, 267, Moskovskaya Str., Brest, 224017, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 3, pp. 401–407, May–June, 1999.     

杂质对量子环上荷负电激子的影响

讨论了在杂质电荷的电场影响下,量子环上荷负电激子X-的能-光谱及其Aharonov-Bohm振荡.当轨道总角动量不守恒的情况下,提出如何按轨道角动量分类构成基矢组并用典型的对角化方法求解体系的本征值和本征矢的方案.该方案计算简单,计算结果令人满意.还讨论了运用等效电荷变换公式和变换图,把位于三维空间的杂质简化为二维平面(或x轴上)的杂质处理,使计算变得更简单,对结果的分析也更明晰.     

Exciton‐Vibrational Couplings in Homo‐ and Heterodimer Stacks of Perylene Bisimide Dyes within Cyclophanes: Studies on Absorption Properties and Theoretical Analysis

The optical properties of a series of three cyclophanes comprising either identical or different perylene bisimide (PBI) chromophores were studied by UV/Vis absorption spectroscopy and their distinctive spectral features were analyzed. All the investigated cyclophanes show significantly different absorption features with respect to the corresponding constituent PBI monomers indicating strong coupling interactions between the PBI units within the cyclophanes. DFT calculations suggest a π‐stacked arrangement of the PBI units at close van der Waals distance in the cyclophanes with rotational displacement. Simulations of the absorption spectra based on time‐dependent quantum mechanics properly reproduced the experimental spectra, revealing exciton‐vibrational coupling between the chromophores both in homo‐ and heterodimer stacks. The PBI cyclophane comprising two different PBI chromophores represents the first example of a PBI heterodimer stack for which the exciton coupling has been investigated. The quantum dynamics analysis reveals that exciton coupling in heteroaggregates is indeed of similar strength as for homoaggregates.     

共轭高分子中激子演化过程的非绝热动力学研究

有机共轭高分子受光激发或被电荷掺杂后可能会产生各种激发状态的激子,激子的演化过程对有机发光光谱有着至关重要的影响.通过非绝热动力学演化的方法模拟了受光激发后有机高分子中激子驰豫的动力学过程,结果表明高激发态激子不稳定,由于电声耦合作用,高激发态激子会持续向低激发态激子演化,同时,低激发态激子的复合发光会发生红移.稳定的激子复合发光光谱中,基态激子发光强度最大,可高达70-80%;第一激发态激子及其它激发态激子发光强度的总和不超过20%.     

Influence of surface charges on the emission polarization properties of single CdSe/CdS dot-in-rods

We report an experimental investigation of the influence of surface charges on the emission polarization properties of single CdSe/CdS dot-in-rods (DRs), which is important for their polarization-based practical applications. By covering the single DRs with N-type semiconductor indium tin oxide (ITO) nanoparticles, the surface of single DRs is charged by ITO through interfacial electron transfer. This is confirmed by the experimental observations of the reduced photoluminescence intensities and lifetimes as well as the suppressing blinking. It is found that the full width at half maximum of histogram of polarization degrees of the single DRs is broadened from 0.24 (on glass) to 0.41 (in ITO). In order to explain the exprimental results, the band-edge exciton fine structure of single DRs is calculated by taking into account the sample parameters, the emission polarization, and the surface charges. The calculation results show that the level ordering of the emitting states determines the polarization degrees tending to increase or decrease under the influence of surface electrons. The surface electrons can induce an increase in the spacing between the emitting levels to change the populations and thus change the polarization degrees. In addition, different numbers of surface electrons may randomly distribute on the long CdSe/CdS rods, leading to the heterogeneous influences on the single DRs causing the broadening of polarization degrees also.     

Size Effect of a Negatively Charged Exciton in a Two-Dimensional Quantum Dot

In this paper we study a negatively charged exciton （NCE）, which is trapped by a two-dimensional （2D） parabolic potential. By using matrix diagonalization techniques, the correlation energies of the low-lying states with L=0, 1, and 2 are calculated as a function of confinement strength. We find that the size effects of different states are different. This phenomenon can be explained as a hidden symmetry, which is originated purely from symmetry. Based on symmetry, the features of the low-lying states are discussed in the influence of the 2D parabolic potential well. It is found that the confinement may cause accidental degeneracies between levels with different low-excited states. It is shown that the effect of quantum confinement on the binding energy of the heavy hole is stronger than that of a light hole.     

有机场致发光中能带模型与分子理论的讨论

在有机场致发光中,能带模型及分子理论从20世纪就存在尖锐的矛盾。在分层优化方案中,经SiO₂加速后的电子能量可以到达10eV,这足以激发发光材料发光,将分层优化方案应用到有机场致发光材料中。发现了固态阴极射线发光(SSCL),经过对它的交叉证明、普适性的验证,肯定了固态阴极射线的发光确实是在发光二极管,无机及有机场致发光之外的一种完全新型的电场诱导的发光。SSCL的特征是在它的光谱中出现短波发光峰,实验证明长波发光峰的减弱是由于电场离化效应。研究了这种效应出现的电压阈值并和SSCL的短波峰出现的电压相比,发现短波峰的出现是在激子的电场离化之后,从而找出了电子处于局域态与扩展态的分水岭,解释了在有机场致发光中能带模型和分子理论并不矛盾,只是适用的条件不同。激子的离化是随电场强度而渐进的变化,因此会有一个两种过程并存的范围。