A method to obtain ground state electroluminescence from 1.3μm emitting InAs/GaAs quantum dots grown by molecular beam epitaxy

1.3μm emitting InAs/GaAs quantum dots(QDs) have been grown by molecular beam epitaxy and QD light emitting diodes(LEDs) have been fabricated.In the electroluminescence spectra of QD LEDs,two clear peaks corresponding to the ground state emission and the excited state emission are observed.It was found that the ground state emission could be achieved by increasing the number of QDs contained in the active region because of the state filling effect.This work demonstrates a way to control and tune the emitting wavelength of QD LEDs and lasers.     

Tensor density matrix theory for determining population and alignment of symmetric top molecule using rotationally unresolved fluorescence

General expressions used for transforming raw laser-induced fluorescence (LIF) intensity into the population and alignment parameters of a symmetric top molecule are derived by employing the density matrix approach. The molecular population and alignment are described by molecular state multipoles. The results are presented for a general excitation-detection geometry and then applied to some special geometries. In general cases, the LIF intensity is a complex function of the initial molecular state multipoles, the dynamic factors and the excitation-detection geometrical factors. It contains a population and 14 alignment multipoles. How to extract all initial state multipoles from the rotationally unresolved emission LIF intensity is discussed in detail.     

Molecular dynamics simulation model of hydrogen recycling on carbon divertor for neutral transport analysis in large helical device

To perform the neutral-transport simulation with processes in which hydrogen molecules contribute to the reaction such as molecular assisted recombination, the parameters of emitted neutral particles at the wall such as the energy distributions and the form (atom or molecule) of emitted neutral particles are necessary as a boundary condition of the calculation. Therefore, in order to provide information of recycled hydrogen on the divertor to neutral-transport code, molecular dynamics simulation of a hydrogen atom injection into a carbon material is performed to obtain the distributions of emission angle and translational energy of emitted hydrogen atoms and molecules. The distributions of rotational and vibrational energies are also investigated in the case of molecular hydrogen emission. Moreover, the quantum rotational state J, and vibrational state v are estimated from the classical value obtained by the simulation.     

母环氨基修饰罗丹明衍生物的结构、热力学性质及其光谱的理论研究

采用DFT/B3LYP方法对3种母环氨基修饰的罗丹明类衍生物的结构进行了全优化,得到此3种化合物的基态和激发态的结构参数、振动光谱、前线分子轨道能量等相关数据,并在基态和激发态几何构型优化的基础上,用TD-DFT方法计算了其气相吸收光谱及发射光谱,全面分析了结构特征对热稳定性、前线分子轨道及光谱性质的影响。结果表明：化合物a末端氨基的扭转运动程度最低,化合物b相对于化合物a,分子共轭及平面程度提高,末端氨基的扭转运动程度增大,气相最大吸收波长及最大发射波长红移,且计算分子中最大发射波长最长,热稳定性最低。化合物c在计算分子中共轭及平面程度、热稳定性、HOMO能量最高,能隙最低,气相最大吸收波长最长。但相对于化合物b末端氨基的扭转运动程度增大,最大发射波长蓝移。     

Fluorescence methods for studying molecular motions

The characteristics of photoluminescence are affected by the molecular motions in the local environment of the excited molecule. Hence, by knowing the lifetime of the excited state, various relaxation times of the molecular motions can be estimated from the emission characteristics. In the present paper the effect of the molecular motions manifested in the fluorescence emission, such as the rotational depolarization of fluorescence, the internal quenching of fluorescence due to internal rotation, and the inter-and intramolecular excimer formation, are reviewed and the possible applications of such phenomena to the study of molecular motions in polymer systems are discussed. The application of fluorescence methods provide unique information about the molecular motions in the nanosecond range in polymer solutions, melts, and solids.     

Coherent electronic coupling versus localization in individual molecular dimers

We have investigated electronic excitation transfer in individual molecular dimers by time and spectrally resolved confocal fluorescence microscopy. The single molecule measurements allow for directly probing the distribution of the electronic coupling strengths due to static disorder in the polymer host. We find dimers where the excitation is delocalized (superradiant emission) while for others emission originates from a localized state. Transitions between delocalized and localized states as observed for a given dimer are attributed to structural fluctuations of the guest-host system.     

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。     

The Effect of Ring Size on the Optical Behavior of Novel Photochromic Push-Pull Dyes

The photophysical behaviors of newly synthesized photochromic dyes have been investigated in different solvents of various polarities using steady-state absorption and emission techniques. It was found that, the absorption and emission spectra of these dyes depend on the ring size and the solvent polarity. The higher values of the dipole moments of the investigated dyes in the excited state than those in the ground state suggest that these dyes can serve as good candidate components of nonlinear optical materials. Additionally, the photoisomerization parameters (percentage of composition of cis isomers and quantum yields of photoisomerization) depend on the polarity and the viscosity of the used solvents as well as the ring size. The molecular motion that occurs in the isomerization process has facilitated the development of molecular devices. Finally, the halochromic behaviors of the investigated dyes promise them to act as acid–base indicators.     

Secondary particle emission from a ferromagnetic binary compound

Secondary ion emission from an ion-bombarded binary compound in the ferro- and paramagnetic states has been studied using experimental methods and molecular dynamics simulations. The experiments were performed with a widely used NiPd binary compound, which was bombarded by obliquely incident 10-keV Ar ions. It is established that the intensity of Ni⁺ and Pd⁺ ion emission from a polycrystalline NiPd sample decreases significantly when it passes from the ferromagnetic to paramagnetic state. This effect is explained by a change in the surface binding energy and density of surface states at the Fermi level and by a cumulative process related to sputtering. The energies and directions of emission of secondary particles from poly- and single-crystalline NiPd samples in the ferromagnetic state have been jointly studied. It is established that the maximum of the polar angular distribution of secondary particles deviates toward the normal to the irradiated surface with a decrease in their energy. A difference in the azimuthal distribution of emitted Ni and Pd particles has been observed during the bombardment of a (001)NiPd crystal face and explained by specific features of correlated collisions. The best agreement of experimental data with the results of molecular dynamics simulations is obtained if the calculations are performed with allowance for an experimentally established modified composition of the three uppermost surface layers [39].     

Angle-resolved high-order above-threshold ionization of a molecule: sensitive tool for molecular characterization

The strong-field approximation for ionization of diatomic molecules by an intense laser field is generalized to include rescattering of the ionized electron off the various centers of its molecular parent ion. The resulting spectrum and its interference structure strongly depend on the symmetry of the ground state molecular orbital. For N2, if the laser polarization is perpendicular to the molecular axis, we observe a distinct minimum in the emission spectrum, which survives focal averaging and allows determination of, e.g., the internuclear separation. In contrast, for O2, rescattering is absent in the same situation.     

Multiphoton Spectroscopy

Abstract

Absorption and cmission spectroscopies, which are widely utilized by chemists, can be classified as one–photon spectroscopy. A molecule is excited from its ground state of energy E₀ to thc excited state of E_e by the absorption of one photon of frequency given by the Bohr's condition (hω=E_e-E₀). The reverse transition is accompanied by the emission of one photon of the same frcquency. Therefore, the molecular state energies can be directly obtained by the photon encrgies absorbed or emitted. Infrared, microwave, electronic absorption, and emission spectroscopies belong to this category of one–photon spectroscopy.     

Spectral Investigations of Solvatochromism and Preferential Solvation on 1,4-Dihydroxy-2,3-Dimethyl-9,10-Anthraquinone

Solvatochromic and preferential solvation of 1,4-dihydroxy-2,3-dimethyl-9,10-anthraquinone (DHDMAQ) have been investigated using optical absorption and fluorescence emission techniques. Optical absorption spectra of DHDMAQ in different solvents show the intra molecular charge transfer band in the region 400–550nm. The observed blue shift with solvent polarity indicates the delocalisation of the excited state, owing to reduction in quasiaromaticity of the chelate rings formed by intra molecular hydrogen bonds, due to electrostatic or hydrogen bonding interaction. This is also confirmed by the observed low oscillator strength and the transition dipole moment. The observed quantum yield of DHDMAQ in different solvents is due to the inter molecular hydrogen bond in the excited state in addition to the intra molecular hydrogen bond. It also reveals from the low oscillator strength, which indicates that the radiative decay is low. Excited state dipole moment of DHDMAQ is calculated by solvatochromic data and it shows a lower value than ground state dipole moment. The preferential solvation parameter shows that in dimethyl formamide (DMF) + ethanol mixture, the DHDMAQ is preferentially solvated by ethanol in DMF rich region and by DMF in ethanol rich region. In the case of DMF + dichloromethane mixture DHDMAQ is preferentially solvated by DMF.     

ESR Detection of Triplet States in Rare Earth Chelates

Abstract

Energy transfer from ligand molecule to ion in rare earth chelates has been assumed to involve a molecular triplet state. ^1,2 These triplet states manifest themselves optically as long-lived T_{π, π? →S}π,π emission if the lowest resonance level of the ion is of higher energy than the molecular triplet. ³ If the resonance level lies below the triplet, longlived emission is absent or severely reduced in intensity. ^4,5     

Lamb–Mössbauer factor of electronically excited molecular states measured by time‐differential Mössbauer emission spectroscopy

The Lamb-Mössbauer Factor (LMF) of molecular crystals is expected to depend on the electronic molecular states by their different intramolecular vibrational frequencies. Revisiting Mössbauer spectra obtained by time differential Mössbauer emission spectroscopy of the low spin compound [⁵⁷Co/Mn(bipy)₃](PF₆)₂ (bipy= 2,2'-bipyridine) a ratio of 1.25 for the LMFs of the low spin ground state and of an excited high spin state decaying in the Mössbauer time window could be evaluated. The difference found is in line with the change of LMF observed for spin crossover compounds where the excited high spin state is populated by the so‐called LIESST effect. The initial population of the high spin state is close to 100%.     

Investigation of Abnormal Long‐Wavelength Fluorescence Emissions Occurring in Binary Organic Nanoparticle Films

In some fluorophores with planar groups, a long‐wavelength emission band different from their native one can sometimes be observed. The main cause of this long‐wavelength band is excimer formation. It is generally accepted that once condensed in the solid state, whether fluorophores can exhibit excimer emission or not depends only on their molecular structure and packing. However, here it is shown that there are exceptions when fluorophores are present in nanoparticles (NPs), where excimer emission can be affected by the environment surrounding the NPs, even in the solid state. It is found that in some binary NP films consisting of fluorophore NPs and other NPs, unusual long‐wavelength bands ascribed to excimer emission can be activated, even though these bands are absent from the photoluminescence spectra of the pure fluorophore NP films. This finding is beneficial to better understand and control excimer emissions. In addition, such a binary NP system provides an ideal platform to investigate the interplay between two fluorophores, because it keeps them effectively separated while maintaining suitable spatial distances for exciton migration and dipole–dipole interactions. This work also provides evidence for the long‐debated origin of the green emission band (g‐band) of fluorene‐based fluorophores.     

A new type of iridium (III) phenylpyrazole complexes: synthesis, photophysical characterization

New heteroleptic iridium(III) complexes (ppz)2Ir(LX), which consist of two cyclometalated ligands ppz(1-phenylpyrazole) together with an ancillary ligand LX (LX= 2-(2'-hydroxylphenyl)benzothiazole (BTZ), 2-(3'-methyl-2'-hydroxylphenyl) benzothiazole (3-MeBTZ), 2-(4'-methyl-2'-hydroxylphenyl) benzothiazole (4-MeBTZ) and 2-(4'-Trifluoromethyl-2'hydroxylphenyl) benzothiazole (4-tfmBTZ)), were synthesized and characterized. The molecular structures and photophysical properties were characterized and analyzed comparatively. The results show that the four complexes have basically similar UV-Vis absorption spectra, fluorescence excitation and emission spectra. Their maximum emission peaks are located at 583-615 nm, and accompanied by a lower intensity emission band around 400 nm. The weak emissions around 400 nm are ascribed to the radi ation transition of single state excition from ancillary ligand BTZ perturbed by metallic ion, and light emission around long-wave-length to the radiation transition of 3MLCT of Ir(BTZ) fragment. While the triplet state 3 MLCT of Ir(ppz)2 fragment might be quenched at room temperature. For all complexes, the excitations with maximum efficiency are located at 250-310 nm, which indicates that main contributor to light emitting is ligand-centered absorption (1pi-pi*) of ppz and BTZ rather than 3MLCT transitions, and thus provides a striking evidence that there is intersystem crossing from 1pi-pi* state to 3MLCT state in these complexes. Compared with Ir(ppz)3, these complexes not only have stronger phosphorescence at room temperature but also their emission color can be tuned by modifying ancillary ligand.     

Y型四能级中的双电磁感应透明和超窄吸收

采用密度矩阵方程．对双光场耦合的分子Y型四能级系统的粒子数分布和吸收特性进行了计算和分析,在此能级系统中得到了双暗态共振和双电磁感应透明．并讨论了相应的物理机制。同时,我们讨论了Y型四能级两个上能级的自发辐射产生的量子干涉效应对电磁感应透明的影响,发现自发辐射干涉相消可以产生超窄线宽和导致探测光的吸收增强,自发辐射干涉相长可以展宽谱线和减弱探测光的吸收,并运用缀饰态理论对以上计算结果进行分析,与采用密度矩阵方程的计算结果一致。     

Cavity-mode selection in spontaneous emission from oriented molecules in a microparticle

We observe preferential cavity-mode selection in spontaneous emission by oriented molecules at the surface of a microparticle. Polarization-analyzed images of a levitated microdroplet containing surface active molecules reveal a well-defined system in terms of molecular position and orientation. The measured fluorescence spectrum is compared with that of a semiclassical emission-rate-enhancement model that treats the coupling between an excited state and Mie resonances as an oscillating dipole interacting with its self-scattered field. By comparing results obtained with this theory with the relative strengths of TE to TM modes measured in the emission spectrum, we show that one can elucidate the heterogeneity of a particle from this resonant structure and determine the orientation of the emission moments relative to the phase boundary.     

Synthesis of Novel Carbazole based Styryl: Rational Approach for Photophysical Properties and TD-DFT

The synthesis and solvatochromic behavior of four novel carbazole based fluorescent styryl dyes were explained. In chlorinated solvents such as DCM and chloroform, these dyes show bathochromic shift in their absorption as well as emission. The styryl dyes 6b and 6c show solid state yellow fluorescence. DFT and TD-DFT computations were performed to study structural, molecular, electronic and photophysical properties of these dyes. The computed absorption and emission wavelength values are found to be in good agreement with the experimental results. The photophysical properties of these 1-styryl carbazole dyes are also compared with the recently reported 3-styrl carbazole dyes. The unique behavior of dye 6d is well explained by its optimized geometry found in the excited state. Ratio of ground to excited state dipole moment of the synthesized novel styryl compounds were calculated by Bakhshiev and Bilot-Kawski correlations.     

Spectroscopic Investigation of Plasma Composition of U-Shaped Argon Stabilized D.C. Arc

The spectroscopic analysis of emitted radiation from the U-shaped argon stabilized d.c. arc is performed when the arc was burning without and in the presence of water aerosol. The special attention is paid to the emission of molecular components. The radial distribution of rotational temperature is obtained from the OH band spectra. The arc plasma composition is also theoretically calculated supposing the state of local thermodynamic equilibrium and compared with experimental results.