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本文基于第一性原理,研究了八个热活化延迟荧光分子的性质,揭示了基团供电子能力对分子几何构型、跃迁属性以及反系间窜越过程的影响.研究结果表明,对于咔唑和氧杂蒽酮组成的一类分子的最低三重激发态(T1)而言,供体基团的二苯胺取代,几乎不会改变供体和受体之间的夹角,但却可以减小供体和受体间的键长.基团供电子能力越强,最高占据分子轨道(HOMO)和最低未占据分子轨道(LUMO)间的轨道重叠度越小,最低单重激发态S1和T1之间的能差(△ES1-T1)越小.此外,供体基团上增加二苯胺能够增加HOMO的离域性,而且能够进一步地减小△ES1-T1.通过计算S1和T1之间的旋轨耦合系数(Hso),发现(<S1|Ĥso|T1>2)/(△ES1-T12)数值越大,反系间窜越速率越大.计算表明八个分子都可能是高效的热活化延迟荧光分子.本文提出了一条高效热活化延迟荧光分子的设计策略,即分离HOMO和LUMO的分布和增加HOMO的离域性能够有效地减小S1-T1能差. 相似文献
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利用含时密度泛函方法计算了两个具有类似结构的传感器分子a和b的氰离子传感机理. 结果证实,传感器分子a在基态和S1态下有着类似的几何构型. 在质子性溶剂水中,氰离子能与传感器分子a发生Michael加成反应,水溶液提供质子,促使最终的α,β-加成产物的生成. 而此加成产物在S1态下会发生构型变化,导致荧光的猝灭. 传感器分子b的S1态与基态构型相比发生了构型扭转,并且在非质子性溶剂乙腈中,也可以与氰离子发生Michael加成反应. 由于乙腈 相似文献
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THE 82S1/2→62D EXCITATION TRANSFER OF RUBIDIUM ATOMS INDUCED BY COLLISIONS WITH GROUND-STATE RUBIDIUM AND HYDROGEN MOLECULES
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The processes of excitation transfer from the 82S1/2 state to the 62D state of rubidium in Rb(82S1/2)-Rb(52S1/2) and Rb(82S1/2)-H2 collisions have been studied experimentally. During irradiating the Rb vapor, mixed with H2, by two light beams for selective stepwise excitation, the Rb 82S1/2→52P3/2 direct fluorescence and the Rb 62D3/2→52P1/2 sensitized fluorescence have been measured as a function of H2 gas pressure. The measurements yielded the cross-sections σ(82S1/2→62D) and σ*(82S1/2→62D) of Rb 82S1/2→62D excitation tranfer induced by collisions with 52S1/2 atom and H2 molecules respectively. The results are discussed in detail. 相似文献
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本文应用坩埚下降法技术在全密封铂金坩埚条件下生长了不同Pr3+离子掺杂浓度的高质量LiLuF4单晶. 测定了单晶体从420 nm至500 nm的激发光谱. 在446 nm光激发下,观察到单晶体480 nm(3P0→3H4)蓝色发射带、522 nm(3P1→3H5)绿色发射及605 nm(1D2→3H4)的红色发射,其对应的平均寿命分别为38.5、37.3和36.8 μs. 其荧光寿命明显大于Pr3+掺杂的氧化物单晶. 同时研究了激发波长和掺杂浓度对发射强度以及色度坐标的影响. 获得最佳的Pr3+浓度为∽0.5 mol%,并分析了环境温度从298 K 到443 K变化对荧光强度的影响. 结果表明随着温度的增加,荧光强度逐步变弱,其中3P0→3H4(480 nm)能级跃迁受温度影响最大,其次是3P1→3H5和1D2→3H4. 相似文献
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THE 82S1/2→62D EXCITATION TRANSFER OF RUBIDIUM ATOMS INDUCED BY COLLISIONS WITH GROUND-STATE RUBIDIUM AND HYDROGEN MOLECULES
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The processes of excitation transfer from the 82S1/2 state to the 62D state of rubidium in Rb(82S1/2)-Rb(52S1/2) and Rb(82S1/2)-H2 collisions have been studied experimentally. During irradiating the Rb vapor, mixed with H2, by two light beams for selective stepwise excitation, the Rb 82S1/2→52P3/2 direct fluorescence and the Rb 62D3/2→52P1/2 sensitized fluorescence have been measured as a function of H2 gas pressure. The measurements yielded the cross-sections σ(82S1/2→62D) and σ*(82S1/2→62D) of Rb 82S1/2→62D excitation tranfer induced by collisions with 52S1/2 atom and H2 molecules respectively. The results are discussed in detail. 相似文献
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激发态双质子转移反应长期困扰着理论和实验科学家并成为了一个悬而未决的热点问题. 本文利用完全活化空间自洽场方法及其二阶微扰理论(MS-CASPT2//CASSCF)系统地研究了典型体系1,8-二羟基-2-萘甲醛(DHNA)的激发态双质子转移反应以及相关的激发态弛豫过程. 在MS-CASPT2//CASSCF水平下,本文优化了三个能量相近但结构不同的S1态互变异构体,即S1-ENOL、S1-KETO-1和S1-KETO-2,以及两个关键的S1/S0锥形交叉点结构,即S1S0-KETO-1和S1S0-KETO-2. 其中,两个极小点S1-KETO-1和S1-KETO-2与实验上观测到的双荧光发射现象密切相关. 本文还利用MS-CASPT2//CASSCF方法计算了双质子转移反应的二维势能面以及从极小点到交叉点结构的线性内插路径;相应计算结果证实了DHNA体系具有分步的激发态双质子转移机制. 具体来说,从S1-ENOL到S1-KETO-1的第一个质子转移过程是无能垒的,而从S1-KETO-1到S1-KETO-2的第二个质子转移过程则需要克服一个大约6.0 kcal/mol的能垒. 此外,由于从S1-KETO-1 (S1-KETO-2)到S1S0-KETO-1 (S1S0-KETO-2)的线性内插路径显示DHNA体系需要翻越一个约为12.0 kcal/mol的能垒,因此DHNA体系将在S1态上停留一段时间并发生双荧光发射现象. 当然,S1/S0锥形交叉点也会促使DHNA体系从S1态内转换到S0态,而这会一定程度上降低DHNA体系发射荧光的效率. 可以通过限制C5-C8-C9-O10二面角旋转来降低体系的内转换效率,进而提高DHNA体系的发光效率. 本工作不仅有助于理解激发态双质子转移机制,还有助于设计具有优异发光性能的新型分子材料. 相似文献
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Guided-Wave Two-Dimensional Acousto-Optic Scanner Using Proton-Exchanged Lithium Niobate Waveguide 总被引:1,自引:0,他引:1
Two-dimensional scanning of a 0.6328 mum guided-light beam has been realized using noncolinear acousto-optic (AO) coplanar Bragg diffraction together with colinear AO guided-mode to substrate radiation-mode conversion in a Z-cut Xpropagation LiNbO3 proton-exchanged (PE) waveguide. The two surface acoustic (SAW) waves utilized are at the center frequencies of 500 and 200 MHz, propagating in the Y and X axes, respectively. Two-dimensional scanning of approximately 720 resolvable light beam spots, namely, 18 40 (horizontal vertical) scanning, has been demonstrated using a light beam of 1.0 mm aperture. The total number of resolvable beam spots can be greatly increased from 720 by simply utilizing SAW transducers of larger bandwidth and a light beam of greater aperture. It should also be possible to significantly increase the diffraction efficiency from 3 % by optimizing the parameters of the PE waveguide and the SAWs. 相似文献
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A review of schemes for multiple access in fiber optic networks shows that a hybrid of wavelength and code division multiple access (WCDMA) combines the best features of both. In particular, the hybrid scheme retains the large information carrying capacity of wavelength division multiple access (WDMA) and flexibility of code division multiple access (CDMA). In this paper WDMA, optical CDMA (OCDMA), and WCDMA networks are discussed. In OCDMA networks, concept of incoherent and coherent coding including inverse decoding and matched filter is introduced. The delay performance of both WDMA and WCDMA networks, under the simple suboptimum access protocols based on cyclic search, is computed. It has been shown quantitatively that tuning delay significantly affects the delay performance of both WDMA and WCDMA networks. Futhermore, delay performance of WCDMA networks is always better than the WDMA networks for the same tuning delay, load, and number of users. 相似文献
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S. G. Nedel’ko M. A. Krysyuk A. L. Apanasenko L. N. Lymarenko Z. T. Moroz 《Journal of Applied Spectroscopy》1997,64(1):55-61
Results of a study of the effect of γ-radiation on the spectral luminescence properties of cadmium tungstate crystals doped
with silver, bismuth, and molybdenum cations are presented. Spectral characteristics of the nondnnnoped crystals are briefly
described. Absorption and photo and X-ray luminescence spectra of the crystals taken before and after exposure to γ-radiation
(5.5·104 Gy) are compared. It is found that the spectral characteristics of the crystals doped with silver, bismuth, and molybdenum
cations do not change markedly after the exposure. The relation between the type of impurity-induced defects, individual characteristics
of the impurity cations, and the character of the effect of γ-radiation on the spectral luminescence properties of impure
crystals is analyzed (preliminarily).
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 1, pp. 55–60, January–February, 1997. 相似文献
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A simple technique of pulse compression, based on the linear chirp compensation of self-phase modulation (SPM) spectra in dispersion shifted fibers, is demonstrated. The optimization procedure is carried out, for a short span of a single-mode fiber, using a parabolic law, which describes the behavior of the squared output pulse width versus the pump peak power in the case of Gaussian pulses. The experimental results give a minimum pulse duration of 233 fs, which is in good agreement with the model. Shorter and coherent pulses, down to 90 fs, have been obtained by inserting an interference filter at the optical output. 相似文献
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The Shanghai Synchrotron Radiation Facility(SSRF)booster ring,a full energy injector for the storage ring,is deigned to accelerate the electron beam energy from 150MeV to 3.5GeV that demands high extraction efficiency at the extraction energy with low beam loss rate when electrons are ramping.Closed orbit distortion(COD)caused by bending magnet field uniformity errors which affects the machine performance harmfully could be effectively reduced by bending magnet location sorting.Considering the affections of random errors in measurement,both ideal sorting and realistic sorting are studied based on measured bending magnet field uniformity errors and one reasonable combination of bending magnets which can reduce the horizontal COD by a factor of 5is given as the final installation sequence of the booster bending magnets in this paper. 相似文献
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We measure the waveform and phase curves of short optical pulses before and after transmission over different lengths of fibers by use of the pulse analyzer with the frequency-resolved optical gating (FROG),and numerically simulate pulse evolution under the experimental conditions.The nonlinear coefficient of the fiber is given by comparing the experimental results with the numerical ones.Difference between the experiment and numerical simulation is analyzed. 相似文献
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Resonance scattering of elastic spherical shell and cylindrical shell while the surrounding fluid medium has absorption is studied. The normal mode solution derived using exact elastic theory and the separation of variables is still applicable. However, the scattering form function has to be modified for the absorbing medium, otherwise the unreasonable result would be obtained. The backscattering form function in the absorbing medium is redefined, and the form function of elastic spherical and cylindrical shell with vacuum or solid matter filled is calculated in various absorption conditions. The results show that the absorption of surrounding fluid leads to notable attenuation of the coincidence resonances in the mid-frequency, but it has a little influence on the low-frequency resonance scattering induced by the filler inside the shell. 相似文献
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A versatile and low-cost single-beam self-referenced phase-sensitive surface plasmon resonance(SPR)sensing system with ultra-high resolution performance is presented.The system exhibits a root-mean-square phase fluctuation of ±0.0028.over a period of 45 min.i.e.a resolution of±5.2×10-9 refractive index units.The enhanced performance has been achieved through the incorporation of three design elements:a true single-beam configuration enabling complete self-referencing so that only the phase change associated with SPR gets detected,a differential measurement scheme to eliminate spurious signals not related to the sensor response,and the elimination of retardation drifts by incorporating temperature stabilization in the liquid crystal phase modulato .Our design should bring the detection sensitivity of non-labeling SPR biosensing closer to that achievable by conventional fluorescence-based techniques. 相似文献
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Ta2O5 films are prepared on BK7 substrates with conventional electron beam evaporation deposition.The effects of SiO2 protective layers and annealing on the laser-induced damage threshold (LIDT) of the films are investigated.The results show that SiO2 protective layers exert little influence on the electric field intensity(EFI)distribution,microstructure and microdefect density but increase the absorption slightly.Annealing iS effective on decreasing the microdefect density and the absorption of the films.Both SiO2 protective layers and annealing are beneficial to the damage resistance of the films and the latter is more effective to improve the LIDT.Moreover,the maximal LIDT of Ta2O5 films is achieved by the combination of SiO2 protective layers and annealing. 相似文献