Excimer emission of crystalline naphthalene

Excimer emission of naphthalene has been observed in microcrystals obtained by grinding single crystals mechanically and in evaporated films. The emission spectrum of the excimer in the microcrystal was equal to that in the evaporated film. The decay times of both excimer emissions were about 140 ns at 77 K. The temperature dependence of these decay times has been interpreted by the distribution of the excimers in thermal equilibrium between two vibrational states.     

Energy transfer in perylene-doped polyvinyl carbazole

Time resolved spectroscopy and fluorescence decay time measurements have been made on thin films of amorphous polyvinyl carbazole (PVK). The value obtained for the excimer fluorescence decay time in the undoped sample is less than that reported previously and a wavelength dependent double exponential decay is observed, which has been seen before only at low temperatures. The observed quenching of the excimer fluorescence decay times in the doped samples is evidence of direct energy transfer from excimers to perylene which is inconsistent with the model of energy transfer by exciton diffusion proposed to explain intensity quenching data. Several models for energy transfer in PVK are discussed and it is shown that the only model which predicts the observed time resolved spectroscopy results requires a long range resonant interaction strength much greater than that obtained theoretically. Several possible reasons for this are discussed.     

Formation mechanism of ethanol-water excimer

The fluorescent spectrum and the excitation spectrum were used to present the cluster molecular structure feature in ethanol-water solutions.Through analyzing the fluorescent characteristics of an excimer,it is proposed that the excimers are formed between the ethanol-water cluster molecules in the excited state and in the ground state.The fluorescent lifetime and the fluorescent intensity decay process give information about the photo-physical and photo-chemical processes of the formation and the dissociation of an excimer.The theoretical calculation and physical analysis coincide with the experimental results.The preliminary conclusion about the structure feature of ethanol-water cluster molecule is that it has a planar one like a sandwich.     

Characterization of the excimers of poly(N-vinylcarbazole) using TRANES

Time-resolved emission spectra (TRES) and time-resolved area normalized emission spectra (TRANES) are exploited to characterize the excimers of poly(N-vinylcarbazole) (PNVC) in toluene and water. The time-resolved study together with the steady state measurements, decipher the fluorescence of the system containing pendant carbazole moieties in the polymer backbone unambiguously. Isoemissive point in the TRANES establishes that there are only two excimers of PNVC, the partially overlapped excimer emitting at high energy and the sandwich type excimer emitting at lower energy, and they are formed exclusively in the photoexcited state. The study substantiates an equilibrium between the two excimers.     

1-羟基-5-十六烷氧基-萘LB膜的荧光光谱研究

１┐羟基┐５┐十六烷氧基┐萘ＬＢ膜的荧光光谱研究李小灵赵冰吴玉清徐蔚青吴英（吉林大学超分子结构与谱学开放实验室长春市１３００２３）Ｓｔｒｕｃｔｒｕｅｏｆ１┐ｈｙｄｒｏｘｙ１┐５┐ｈｅｘａｄｅｃｙｌｏｘｙ┐ＮａｐｈｔｈａｌｅｎｅＬＢＦｉｌｍｓＳｔｕｄ...     

Immobilization of pyrene via diethylenetriamine on quartz plate surface for recognition of dicarboxylic acids

A novel photo-luminescence film has been prepared by immobilizing pyrene on a quartz plate surface via diethylenetriamine. Imino structure was intentionally introduced into the long flexible spacer due to their hydrogen bond forming abilities with carboxylic acids. It has been found that the film shows combined monomer and excimer emission of pyrene both in wet and dry states. Steady-state and time-resolved fluorescence emission measurements demonstrated that the excimer emission mainly came from direct excitation of ground state dimers, and/or monomers in aggregated state. The structures of the excimers formed during the excitation are mixtures of “standard excimers” and “distorted excimers” of the fluorophore moieties. Fluorescence lifetime measurements showed that the decay of the film is complex, and a four exponential fit is necessary for getting a satisfied result. The photophysical behavior of the present film could be rationalized by employing the model proposed before. Sensing property studies showed that the emission of the film is sensitive to the presence of dicarboxylic acids, including ethanedioic acid, malonic acid, etc. In contrast, presence of monocarboxylic acids, such as formic acid and acetic acid, had little effect upon the fluorescence emission of the film. Compared with the films taking ethylenediamine or 1,3-diaminopropane as their spacer component, introduction of diethylenetriamine into the spacer improved the performance of the film greatly. In addition, the sensing process is reversible, and the film is stable within a number of months provided it is properly preserved. These characteristics showed that the film is worthwhile for further exploration.     

Steady state and time-resolved studies of pyrene in solution and in single microcrystals

Single microcrystals of pyrene have been studied by steady state and time resolved fluorescence microscopy. The fluorescence spectra of microcrystals exhibit vibrational structure unlike the broad spectrum observed in pyrene excimer. A risetime is observed in the decay curves of the concentrated solutions, indicating the excimer formation. In contrast, the fluorescence decay profiles of the single microcrystals are nonexponential in nature and the decay times vary with their size and the wavelength of emission. This behaviour has been explained mainly by considering the pyrene dimer stabilized in the ground state.     

Zn2准分子的形成及其发射特性

通过光学抽运Zn(4s¹S₀—4p³P₁)共振线,在充有惰性气体的Zn蒸气中观察到两个连续的发射谱带。实验辨认它们可能归属于Zn₂准分子³∑_u⁺态,这与理论预言一致。研究谱带的时间与温度特性,以及惰性气体对谱带发射的影响。给出分子形成速率的上限和猝灭速率。结果表明,惰性气体分子在Zn₂准分子的形成及衰变中起了主要作用。 关键词：     

有关离子准分子的研究和探讨

针对碱金属卤化物离子准分子（AX）^＋、稀有气体碱金属离子准分子（RgA)^＋、稀有气体卤化物离子准分子（RgX)^＋、同核和异核稀有气体离子准分子的荧光谱以及Cs^2 F^-离子准分子的光学增益现象,本文从光谱学和动力学的角度描述这些离子准分子的研究情况,探讨实现离子准分子布居反转的关系因素。     

Comprehensive kinetic model for electron-beam-excited XeCs+ ionic excimers

A theoretical model that accounts for fundamental plasma processes leading to the formation and decay of XeCs⁺ ionic excimers in high-pressure electron-beam-excited Ar/Xe/Cs mixtures was developed. Numerical calculations based on the model were performed. For atmospheric gas mixtures, the model predicts an intrinsic efficiency (energy stored in upper state/energy deposited) of 18%. Model calculations also indicate that while XeCs⁺ was predominantly formed via the rare-gas ion (Xe⁺) channel over the entire e-beam duration, the rare-gas metastable (Xe*) channel assumes dominance in the afterglow period.     

Gain properties of a wide aperture X-ray pre-ionized excimer amplifier

A wide aperture, X-ray pre-ionized discharge pumped excimer laser was comparatively studied as oscillator and amplifier with XeCl and KrF as the active gases. With XeCl (KrF), an oscillator output energy of 3J (1 J) and a small-signal gain coefficient of 11%cm^–1 (6%cm^–1) were measured. The beam size was 6×5 cm². For smaller beam widths (obtained by limiting the pre-ionized region), both excimers showed considerably higher gain. The dependence of output parameters on the X-ray dose was studied for both excimers.     

Fluorescence spectrum characteristic of ethanol--water excimer and mechanism of resonance energy transfer

The steady-state fluorescence spectrum characteristic of ethanol--water excimer has been studied in this paper. By analysing the features of the sharp emission spectrum with fine structures in a shortwave band and the characteristics of the broad and featureless fluorescence peaks in the longwave band, one can conclude that the excimers are formed between the new ethanol--water cluster molecules in the excited state and the ground state through the interaction among different chromophores. The excitation spectra in the two fluorescence bands have been studied, and their emission mechanisms have been ascertained based on the energy transfer theory. Furthermore, the critical distance of the resonance energy transfer has been calculated.     

Steric effect of methyl, methoxy, and ethyl substituents on the excimer formation of naphthalene on Al2O3(0 0 0 1)

Structural relaxation of molecules on surfaces can be monitored by observing the spectral evolution as increasing amount of thermal energy is made available. Naphthalene forms excimers in the excited state when amorphously prepared, but relaxes to a more ordered state when heated. Substituent groups on the naphthalene can substantially alter the available pathways during the thermally induced structural relaxation, and is reflected in the formation of excimer or trap fluorescence. A general correlation was determined for the naphthalene substitution with methyl, methoxy, and ethyl groups on the 1- and 2-positions with the pathway taken by the molecular adlayer.     

Electronic spectroscopy of highly-polar aromatics. V. The polar excimer of N,N-dialkyl-p-cyanoaniline

The fluorescence spectra of N, N-dialkyl-p-cyanoanilines in fluid media have been re-examined. The long-wavelength fluorescence, previously attributed to a solvated ¹L_a → ¹A₁ fluorescence, is interpreted as an excimer fluorescence, an assignment which is supported by concentration dependence studies and quenching experiments. The temperature dependence of the excimer/ monomer fluorescence intensity ratio indicates that excimer formation is a diffusion controlled process. The binding energy of the excimer is found to be independent of the nature of the solvent and to be smaller than those values estimated for excimers of polycyclic aromatic hydrocarbons. Solvent viscosity, solvent polarity and specific solvent-solute interactions affect the excimer/monomer fluorescence intensity and these effects are interpreted. The geometry of the excimer is also discussed.     

Excimer emission from glassy films of some aromatic hydrocarbons

The fluorescence emission spectra and fluorescence decay times of amorphous films prepared by evaporation of a number of aromatic hydrocarbons on to a substrate cooled with liquid nitrogen were measured. The fluorescence of such films appears to originate from sites where the interaction between neighbouring molecules is of the same kind as that present in the well-known excimer state. The density of such sites is found to be so high as effectively to prevent energy migration. Some interesting exceptions to this behaviour are noted and comparisons drawn with experimental data reported for excimer formation in solution and in the crystalline phase.     

Structural and photophysical properties of anthracenyl and carbazolyl groups in silicone-based polymers

This paper describes a simple methodology to attach luminescent groups (anthracenyl and carbazolyl) to polysiloxanes (silicone), using hydrosilylation reactions between the Si–H groups from the silicone precursor to vinyl derivatives of the lumophores. The photophysical properties of these luminescent silicones were studied using both steady-state and dynamical photoluminescence spectroscopy. A strong correlation was obtained between the structural characteristics of the anthracenyl- and carbazolyl-based polysiloxanes, depending on the amount and the position of the Si–H bonds in the silicone precursors. For sparsely distributed Si–H groups, both the anthracenyl-labeled and carbazolyl-labeled polysiloxanes showed photophysical properties (fluorescence spectrum and fluorescence decays) similar to those of 1-alkyl anthracenyl and 1-alkyl carbazolyl derivatives, respectively. Nevertheless, for closely spaced Si–H groups, emission and decay are different. The presence of excimers was observed for anthracenyl but not for carbazolyl polysiloxanes. This latter observation is quite different from that observed for carbon-based polymers for which the carbazolyl excimer formation is a very common process probably due to the differences in the silicone structure.     

Generation of excimer emission in dielectric barrier discharges

Dielectric barrier discharges (silent discharges) are used to excite a large number of excimers radiating in the VUV, UV or visible spectral range. The excited species include rare-gas dimers, halogen dimers as well as rare-gas halogen excimers and mercury halogen excimers. In many cases narrow-band UV radiation of typically 1–17 nm halfwidth and remarkable efficiency (1–10%) could be generated. Thus, dielectric barrier discharges provide a simple, versatile arrangement to study the basic reaction kinetics of excimer formation and also bear a substantial potential for large-scale industrial UV processes.     

Excimer emission from evaporated pyrene films

Emission spectra and decay times of fluorescence of pyrene thin films prepared by evaporation onto glass substrate at low temperatures were measured. The band positions of the excimer emission from the films evaporated onto substrates at temperatures below about 200 K, are found to the lower energy side of those of the crystal. The decay time of excimer emission in a film prepared by evaporation onto a substrate cooled with liquid nitrogen is about 100 ns at 85 K and is shorter than that of the crystal. These results are discussed in relation to an amorphous structure in the pyrene evaporated thin films. The energy transfer was also studied in evaporated pyrene films containing perylene as a dopant. The results are explained in terms of excimer exciton diffusion through the crystalline structure in the film.     

Irradiation-induced luminescence enhancement effect of ZnS:Mn(2+) nanoparticles in polymer films

The effects of irradiation-induced luminescence enhancement by ZnS:Mn(2+) nanoparticles in poly(vinyl butyral) films are reported. The luminescence intensity increases several times when fresh samples are irradiated by a 248-nm excimer laser. The decay time also increases with exposure time. The increase in the initial intensity of the slow component of luminescence makes the main contribution to the enhancement effect. A tentative model is proposed in which the efficiency of the energy transfer to Mn(2+) ions increases with exposure. States at interfaces are expected to play an important role in this process.     

An anomalous emission excited near the absorption edge of pyrene crystals

Emission spectra and decay times of the fluorescence excited at the absorption edge region in pyrene crystals were measured. At liquid nitrogen temperature, the fluorescence under the excitation at 390 nm is considered as the excimer emission and its band peak shifts a little to the short wavelength in comparison with that of the excimer emission under the excitation at 360 nm. The emission decay times under the excitation at the 390 nm and 360 nm are about 155 ns and 180 ns, respectively, at liquid nitrogen temperature. The former decay time changes its value abruptly near 127 K. This abrupt change of the decay time may be due to the phase transition in pyrene crystals.