Quenching of the fluorescence of solutions of complex molecules by nonradiative transfer of electronic-excitation energy to a saturable acceptor

The study puts toward a theoretical model describing the fluorescence parameters for concentrated solid solutions consisting of complex molecules of two types (donor-acceptor) with nonradiative transfer of electronic-excitation energy with intense pulse excitation. Consideration is given to the dynamics of quenching of the luminescence of the donor molecules due to transfer of electronic-excitation energy to the acceptor molecules. Numerical results are presented in the form of approximation formulas. To whom correspondence should be addressed. Belarusian State University, 4, F. Skorina Ave., Minsk, 220050, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 5, pp. 652–656, September–October, 1999.     

Femtosecond luminescence decay due to exciton energy transfer in single-walled carbon nanotube bundles

We investigated luminescence decay kinetics in single-walled carbon nanotubes in large bundles excited by femtosecond pulses. The time constant of luminescence decay becomes longer with decrease in photon energy: 40 fs at 1.2 eV and 380 fs at 0.6 eV. This behavior is explained by exciton energy transfer from an excited to neighboring tubes.     

Investigation on luminescence and energy transfer in Tb-doped lead telluroborate glasses

This work reports on the visible luminescence properties and energy transfer processes responsible for non-exponential nature of the decay curves and also quenching of luminescence intensity of the ⁵D₃→⁷F_J transitions of Tb³⁺ ions in lead telluroborate (PTB) glasses containing different Tb³⁺ concentrations. The XRD and FT-IR spectra were measured to study the glassy nature and composition of the prepared glasses. The radiative properties are determined using the Judd-Ofelt theory to judge the suitability of studied glasses as practical photonic material. These parameters suggest that the PTBTb20 glass has the potential to produce intense green emission (544 nm) through the ⁵D₄→⁷F₅ transition.     

Trapping and self-trapping in ytterbium-doped oxides with charge transfer luminescence

Temperature dependence of the charge transfer luminescence (CTL) of Yb-doped yttrium aluminum garnet Y₃Al₅O₁₂-Yb (YAG-Yb) and Yb-doped lutetium aluminum perovskite LuAlO₃-Yb (LuAP-Yb) crystals under X-ray excitation and their thermostimulated luminescence are investigated in the temperature range 30-350 K and compared to those of undoped crystals. Simulation using a set of kinetic equations describing the processes of creation of excitons, electron-hole pairs, their trapping and self-trapping, radiative relaxation and quenching is presented for the systems under investigation to analyze qualitatively two different types of experimentally observed temperature dependences: CTL yield decline with the temperature decrease below 110 K as in case of YAG-Yb and constant yield in the same temperature range as in case of LuAP-Yb.     

Spectral characteristics of luminescence of solutions of complex molecules under conditions of electronic excitation transfer to a saturable acceptor in the case of inhomogeneous broadening of electronic energy levels

Spectral characteristics of solutions of complex molecules under conditions of inhomogeneous broadening of energy levels are considered in the case when the nonlinear dependence of the population of molecular states on the excitation intensity is determined not by saturation of molecular levels but by exchange of the electronic excitation energy with the environment. Calculations have shown that the dependence of the position of the fluorescence spectrum on the excitation frequency is nonmonotonic in solutions of the type and varies substantially with the excitation intensity. Belarusian State University, 4, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 2, pp. 164–168, March–April, 1997.     

Influence of donor-donor transport on excitation energy transfer

Energy migration and transfer from acriflavine to rhodamine B and malachite green in poly (methylmethacrylate) have been investigated using the decay function analysis. It is found that the influence of energy migration in energy transfer can be described quite convincingly by making use of the theories of Loring, Andersen and Fayer (LAF) and Huber. At high acceptor concentration direct donor-acceptor transfer occurs through Förster mechanism.     

Luminescence and energy transfer in europium Tellurite anti-glass phases

The luminescence and energy transfer properties of two lower symmetrical europium tellurite anti-glass phases are reported, viz. Eu_1.79TeO_x, which has a pseudo-tetragonal structure, and Eu_1.08TeO_x, which has a monoclinic ordered crystal structure.

In the pseudo-tetragonal phase the Eu³⁺ ions occupy two major types of sites. In the monoclinic phase there are at least seven different crystallographic sites available to the Eu³⁺ ions. At low temperatures transfer of excitation energy to the sites with the lowest ⁵D₀ energy levels occurs, and only these sites luminesce. Above 10 K backtransfer to higher ⁵D₀ levels takes place.

The energy migration process, which becomes important at temperatures above 20 K for the pseudo-tetragonal phase and above 10 K for the monoclinic phase, is two-phonon assisted. For both compounds the assistance mechanism up to about 50 K is two-site non-resonant, and at higher temperatures it is one-site resonant.     

CdTe量子点与罗丹明B水溶液体系下的双光子激发荧光共振能量转移

采用时间分辨荧光光谱技术研究了在双光子激发下不同尺寸的量子点与罗丹明B 之间的荧光共振能量转移. 研究结果表明, 在800 nm的双光子激发条件下, 体系间能量转移效率随着供体吸收光谱与受体荧光光谱的光谱重叠程度增加而增加; 理论分析表明, 供体和受体间的Förster半径增加是导致其双光子能量转移效率增大的物理原因. 同时, 研究了罗丹明B浓度对荧光共振能量转移效率的影响. 研究结果表明, 量子点的荧光寿命随着罗丹明B浓度的增加而减小; 量子点与罗丹明B之间的荧光共振能量转移效率随着罗丹明B浓度的增加而增加; 当罗丹明B浓度为3.0×10^-5 mol·L^-1时, 双光子荧光共振能量转移效率为40.1%.     

铈铕共掺高钆氧化物玻璃的发光性能及能量传递效应

在还原气氛下, 采用高温熔融法制备了Eu²⁺/Ce³⁺共掺的高钆氧化物玻璃. 荧光性能测试显示, Ce³⁺能够有效地敏化Eu²⁺的发光, 使Eu²⁺的发光强度增强了2.3倍; 测试对比了Ce³⁺ 发光的荧光寿命随Eu²⁺的掺入前后的变化情况, 计算得出Ce³⁺→Eu²⁺ 的能量传递效率可达61.5%, 并进一步探讨了其能量传递机理. 研究表明: 在高钆氧化物玻璃中, 采用Eu²⁺ 和Ce³⁺ 共掺的方法可有效地增强Eu²⁺ 的发光性能和闪烁性能. 关键词： 发光玻璃 能量传递 荧光寿命     

Ho3+离子掺杂单颗粒氟化物微米核壳结构的上转换发光特性

构建核壳结构可有效降低材料的表面缺陷及实现掺杂离子的可控区域分布,已成为目前增强及调控材料发光特性的有效手段之一.为此,本文以外延生长技术,构建了一系列NaLnF₄(Ln=Y,Yb,Ho)@NaLnF₄(Ln=Y,Yb)核壳微米结构,并实现了Ho³⁺离子上转换发光的增强及可控调节.借助共聚焦显微光谱测试系统,在980 nm近红外激光激发下,研究Ho³⁺离子在不同单颗粒核壳结构中的上转换发光特性.结果表明,当包覆NaYF₄惰性壳时,NaYF₄:Yb³⁺/Ho³⁺及NaYbF₄:Ho³⁺微米棒的上转换发射强度均得到了明显增强,而NaHoF₄@NaYF₄微米核壳结构的发射强度却没有发生明显的变化.当在其NaYF₄惰性壳中引入Yb³⁺离子时,NaYF₄:Yb³⁺/Ho³⁺,NaYbF₄:Ho³⁺及NaHoF₄微米核壳结构的发射强度及红绿比均再次得到了明显增强.基于对其光谱特性及动力学过程的研究,其发射增强主要由于壳层中的Yb³⁺离子通过能量迁移及传递过程有效地提高Ho³⁺离子激发,进而在双向协同的作用下实现其发光有效增强及色彩调控.由此可见,对于微米晶体而言,构建其不同的核壳结构不仅可实现其发光有效增强,且可根据掺杂离子的不同及其区域分布实现光谱的精准调控,为拓展高效发光特性的微米晶体在防伪、微纳光电器件等领域的应用提供新途径.     

光纤布拉格光栅非线性传输特性的数值研究

 回顾了光纤布拉格光栅非线性耦合模方程的数值求解方法,分析了基于隐式龙格 库塔方法的预报校正系统的特点。为实现简捷、高效、高阶精度的光纤布拉格光栅非线性耦合模方程的数值仿真,设计了基于连分式修正法的预报-校正系统并与基本方法进行了对比。采用该方法可以极大地加长光栅的分段长度以节约计算时间,同时也不存在仿真过程中因计算方法产生的不收敛现象,误差对比分析表明该方法能够准确地模拟光栅的非线性传输特性。为解决静态和动态情况下仿真方法不统一并避免数值计算引起的冲击响应,根据光栅中光波传输的物理过程建立了静态和动态情况下统一的数值仿真模型并研究了仿真中所采用的多种技术,利用这些技术能够有效地仿真连续波和脉冲输入情况下光纤布拉格光栅的非线性传输特性。     

Förster resonant energy transfer in quantum dot layers

Förster resonant energy transfer (FRET) in quantum dot (QD) layer structures has been analyzed. Small and large colloidal CdTe QDs were used as donors and acceptors, respectively. A FRET theory for random donor/acceptor distributions in two dimensions, taking into account exclusion zones around the donors, was applied to characterize FRET in a mixed monolayer. The exclusion zones provide a possibility to include the QD size in the FRET analysis and to determine its impact on the FRET efficiency. The acceptor concentration dependence of the FRET efficiency can also be described within this theory. In a separate donor/acceptor layer structure the distance dependence of the FRET efficiency as well as the acceptor enhancement was investigated. Both were found to agree well with the model of FRET between donor and acceptor layers.     

Tm3+/Yb3+共掺碲铅锌镧玻璃的能量传递和上转换发光

制备了Tm³⁺/Yb³⁺共掺TeO₂-PbO-ZnO-La₂O₃玻璃，研究了玻璃红外吸收光谱和980 nm激光抽运下上转换发光光谱，分析了上转换发光机制.基于Tm³⁺和Yb³⁺的能级图及上转换机制建立了速率方程，得出了稀土离子各能级的粒子数分布密度以及Tm³⁺与Yb³⁺之间的能量转移系数C_bi(i=0, 1,3).结果表明，随着PbO加入，Yb³⁺:²F_5/2与Tm³⁺:³H₄间的能量转移不断增加，上转换蓝光的发光强度明显增强. 关键词： 碲酸盐玻璃 上转换发光 能量传递 速率方程     

Luminescence excitation spectra and characteristics of luminescence centers with overlapping absorption bands

For an ensemble of different types of luminescence centers with overlapping absorption bands, with no restrictions on the optical densities, we have obtained relations describing the luminescence excitation spectra for each type of center. We consider transformations of the relations in some limiting cases. We suggest a procedure for using the equations obtained to determine the characteristics of the luminescence centers. Some of these procedures have been experimentally implemented in study of intrinsic radiation color centers in lithium fluoride crystals. We have determined the ratios of the luminescence quantum yields for F₂ and F₃⁺ color centers, and we have observed that a major role is played by nonradiative transitions in deactivation of the first excited singlet state of F₃⁺ centers. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 365–371, May–June, 2008.     

ACaPO_4:Eu~(2+),Nd~(3+)(A=Li,K,Na)的近红外发光与能量传递

采用高温固相法制备了ACaPO4∶Eu2+,Nd3+(A=Li,K,Na)系列近红外发光材料,研究了材料中Eu2+对Nd3+的近红外发光的敏化作用。发现共掺Eu2+后,材料的Nd3+的近红外发光显著提高。同时考察了ACaPO4∶Eu2+可见荧光性能、ACaPO4∶Eu2+,Nd3+近红外荧光发光性能及其荧光寿命,研究了不同Eu2+的发射波长对Nd3+近红外发光的敏化效果,分析探讨了ACaPO4体系中Eu2+-Nd3+之间的能量传递机理。在ACaPO4(A=Li,K,Na)中,随基质的不同,Eu2+的发射峰有逐步红移的现象,与Nd3+的不同激发峰重叠程度也会发生明显的变化,表明Eu2+的荧光发射波长是影响能量传递的一个重要因素,可以推测发射波长处于500～550 nm之间的Eu2+对Nd3+近红外发光具有最佳的敏化效果。     

Collision-induced rovibrational energy transfer in small polyatomic molecules: the role of intramolecular perturbations

ABSTRACT

Various forms of time-resolved optical double-resonance spectroscopy facilitate rotationally resolved measurements of collision-induced intramolecular vibration-to-vibration (V–V) energy-transfer processes, which take a gas-phase polyatomic molecule from one distinct rovibrational energy level to another. Of longstanding mechanistic interest are questions concerning the extent to which such V–V energy transfer (ET) may be influenced by intramolecular perturbations – notably Fermi resonance (and other anharmonic mixing effects) and Coriolis coupling – within polyatomic molecular rovibrational manifolds of interest. It is evident that quantum-mechanical interference effects can arise, either inhibiting or enhancing the probability of collision-induced ET in perturbed rovibrational manifolds of certain small gas-phase polyatomic molecules, notably CO₂, D₂CO and C₂H₂. This article focuses on a blend of high-resolution rovibrational spectroscopy (characterising initial and final molecular levels and their intramolecular perturbations) and collision dynamics (with colliding molecules defined in terms of isolated-molecule spectroscopic basis states). It aims to offer fresh insights and to consider some apparent mechanistic anomalies (e.g. collision-induced quasi-continuous background effects in the 4ν_CH rovibrational manifold of C₂H₂). Various reported experiments and related theoretical treatments are critically re-examined, in order to pose and address mechanistic questions some of which still challenge detailed understanding.     

Optical bistability in an all-optical fiber nonlinear fabry-perot resonator with linear absorption

An all-optical fiber nonlinear Fabry-Perot resonator is proposed. The steady-state model for describing this resonator is developed. The transmission and refection bistabilities are shown numerically. Our results show that the bistability in this system is similar to that in a normal nonlinear Fabry-Perot etalon, except that the characteristics of the bistability can be changed not only by the cavity length but also by the phase shifts of the fiber loop mirrors.     

A sensitive fluorimetric method for determination of trace amounts of nitrite based on luminescence energy transfer

An efficient luminescence energy transfer (LET) system based on terbium(III)-sodium hexametaphosphate (Tb/SHMP) chelates as donor and 4-((4-(2-aminoethylamino)naphthalen-1-yl)diazenyl)benzenesulfonic acid dihydrochloride (ANDBS) as acceptor was developed for sensitive determination of trace nitrite. Stable and strong fluorescence Tb/SHMP chelates were prepared in aqueous solution. Based on Griess Reaction, ANDBS was generated by the quantitative reaction of nitrite, sulfanilamide and N-(1-naphtyl)-ethylenediamine dihydrochloride (N1NED). The degree of the overlap was effective for LET between the emission spectrum of Tb/SHMP chelates and the absorption spectrum of ANDBS. Based on the luminescence intensity quenching of Tb/SHMP chelates in proportion to the trace amounts of nitrite, a new assay for the selective and sensitive determination of nitrite was developed. Under the optimum conditions, the linear calibration graph was obtained with a linear range of 0.00040-0.20 μg mL⁻¹ (R=0.99657). The detection limit of was 0.00010 μg mL⁻¹ (R=0.99657). The method was applied successfully to the determination of nitrite for synthetic samples.