ZBLAN玻璃中Pr3+掺杂离子3P0和1D2能级的发光特性和寿命

对ZBLAN氟锆酸盐玻璃中Pr³⁺掺杂离子³P₀和¹D₂能级的寿命和发光特性进行了较详细的光谱学研究。首先测量了两种掺杂浓度(质量分数分别为1×10^-3,5×10^-3)的Pr³⁺:ZBLAN玻璃的吸收光谱,然后运用时间分辨激光光谱技术测量了³P₀和¹D₂能级在激光单光子共振激发下的荧光发射谱和能级寿命。将不同荧光发射谱带的强度和文献报道的Judd Ofelt理论计算辐射跃迁几率数值做了比较分析,证明了文献中理论计算结果的可靠性。由于浓度猝灭效应,在相同的激发条件下,掺杂浓度为1×10^-3样品的荧光发射强度明显大于5×10^-3样品的荧光发射强度。但是从我们的测量结果看,掺杂浓度对³P₀和¹D₂ 的能级寿命值无显著影响。掺杂浓度为1×10^-3时,Pr³⁺离子³P₀和¹D₂能级的寿命值分别为46,322μ_s。     

两种高分子化锌卟啉络合物与特丁津相互作用的光谱性能研究

将苯基卟啉(PP)功能化的聚甲基丙烯酸缩水甘油酯(PGMA)即PP-PGMA和羟基苯基卟啉(HPP) 功能化的PGMA(HPP-PGMA)分别与锌离子发生络合反应,制得高分子化的苯基锌卟啉ZnPP-PGMA或羟苯基锌卟啉ZnHPP-PGMA。采用¹H-NMR对ZnPP-PGMA和ZnHPP-PGMA的化学结构进行了表征,用紫外-可见光谱法、荧光光谱法研究了其光谱性能。将ZnPP-PGMA或ZnHPP-PGMA与特丁津作用,研究特丁津对其光谱性能的影响。研究结果表明:高分子化的金属卟啉ZnPP-PGMA和ZnHPP-PGMA都具有强的光谱性能,相对于PP-PGMA和HPP-PGMA,其电子吸收光谱Soret吸收带红移,荧光发射峰蓝移。ZnPP-PGMA和ZnHPP-PGMA分别与特丁津作用后,ZnPP-PGMA的紫外光谱发生一定程度的红移,且ZnPP-PGMA和ZnHPP-PGMA发生明显的荧光猝灭现象。随着特丁津浓度的增大,ZnHPP-PGMA发生荧光猝灭的程度增大。     

Electron–hole recombination luminescence in LiYF4:U single crystal

Photoluminescence (PL), photostimulated luminescence (PSL), thermally stimulated luminescence (TSL) and electron paramagnetic resonance (EPR) studies were carried out on LiYF₄:U⁴⁺ and pure LiYF₄ crystals. The PL and EPR investigations have identified the presence of Eu³⁺, Tb³⁺ and Gd³⁺ ions in both of these crystals possibly due to their existence in the starting materials. The luminescence observed during afterglow, PSL and TSL revealed that emission occurs at wavelength positions 382, 413, 437 and 544 nm, which are characteristic of Tb³⁺ ions. The present investigations using PSL and TSL in combination with PL studies before and after gamma irradiation have revealed that selective energy transfer to Tb³⁺ ions occurs during electron–hole recombination processes like PSL and TSL. Even though other luminescent ions (U⁴⁺ and Eu³⁺) are present in the system and U⁴⁺/U³⁺ ions are participating in electron capture/release processes, the selective energy transfer results in Tb³⁺ ions acting as luminescence centers.     

High resolution Fourier transform infrared spectroscopy using a high temperature argon arc source

Application of a high temperature wall-stabilized argon arc source (HTAAS) for high resolution near- and mid-infrared Fourier transform infrared spectroscopy (FTIR) has been investigated. Spectra of N₂O, NH₃ and the complex OC-HCl were recorded at maximum apodized instrumental resolution (0.004 cm⁻¹). The signal to noise (S/N) ratio of these molecular absorption transitions were compared with corresponding spectra recorded using a 1520(30) K globar source. At 7.6 μm, recorded ¹⁴N₂ ¹⁶O transitions are consistent with a HTAAS at approximately 10,000 K and an enhancement of 12.6 in recorded S/N ratios with respect to the latter globar source. Such results demonstrate a significantly enhanced performance for specific FTIR applications such as high resolution static gas phase spectroscopy and molecular spectroscopy in supersonic jet expansions, and potentially for infrared microscopy.     

OH-对Er掺杂的亚碲酸盐氟氧化物玻璃上转换发光的影响

Er掺杂的亚碲酸盐玻璃具有很好的上转换性质,加入氟化物在干燥的气氛下可以制备低OH^-根含量的氟氧化物玻璃,同样组分在湿润的气氛下,仍有较高的OH^-根含量.通过傅里叶红外吸收光谱、荧光衰减曲线及上转换光谱研究了在干燥和湿润气氛下,亚碲酸盐氟氧化物玻璃的OH^-含量,以及对上转换发光的影响.在干燥的气氛下制备的亚碲酸盐玻璃的OH^-浓度为0.017×10²⁰cm^-3是湿润的气氛下制备玻璃中的1/15,其543nm绿光上转换效率增加了2.4倍.     

Er~(3+)掺杂Na_5Lu_9F_(32)单晶体的红外光学特性

采用坩埚下降法成功地生长了Er~(3+)离子掺杂的Na_5Lu_9F_(32)(NLF)单晶体。测定了单晶体在400~2 500nm波段的吸收光谱与2.5~25μm红外波段的透过光谱。Na_5Lu_9F_(32)单晶体在400~7 150 nm宽波段范围具有好的光学透过性,在该波段的透过率达到90%。在透过光谱中几乎观察不到2.7μm中红外波段的吸收,说明单晶体中OH~-离子的含量极低。根据测定的吸收光谱,通过Judd-Ofelt理论计算了Er~(3+)在单晶体中的光学强度参数Ω_t(Ω_2=2.08,Ω_4=2.07,Ω_6=0.75),以及相应的辐射跃迁速率、荧光分支比和荧光寿命。根据Futchbauer-Ladenburg公式估算了样品的发射截面大约分别为1.42×10~(-20)cm~2(~4I_(13/2)→~4I_(15/2))和1.66×10~(-20)cm~2(~4I_(11/2)→~4I_(13/2))。在980 nm半导体激光器(LD)激发下,研究了单晶体的近红外1.5μm与中红外2.7μm的发射光谱特性。     

理论研究OH+离子电子态光谱及跃迁性质

采用高精度的内收缩多参考组态相互作用方法（icMRCI）计算OH⁺离子基态和低激发态的势能曲线和A³П-X³Σ^-跃迁体系的跃迁偶极矩。计算过程中考虑了能量的Davidson修正（+Q）效应和标量相对论修正。根据势能曲线,通过求解核的一维Schrödinger方程得到OH⁺的光谱参数。通过计算A³П-X³Σ^-体系的跃迁偶极矩研究这一跃迁体系的Einstein系数、F-C因子。研究了A³П（ν'=0~6）态的跃迁辐射寿命,结果显示其数量级为10^-6 s。     

13Cu、65Cu和15N标记的二(2-羟基苯乙酮肟)-铜(Ⅱ)配合物的ESR波谱研究

本文解析了同位素标记的⁶³Cu-¹⁴N-HAP,⁶⁵Cu-¹⁴N-HAP,⁶³Cu-¹⁵N-HAP。⁶⁵Cu-¹⁵N-HAP,和Cu-¹⁵N-HAP,等五种配合物在四氢呋喃中,在77K温度下测得的分辨较好的ESR波谱。从图上不仅得到了⁶³Cu和⁶³Cu的超精细分裂,而且还得出分辨较好的¹⁴N和¹⁵N的超超精细分裂。比较合理地确定了g_x,g_y,g_z;A_x⁶⁵,A_y⁶⁵,A_z⁶⁵和A_x⁶³,A_y⁶³,A_z⁶³以及A_⊥¹⁵,A_⊥¹⁵和A_⊥¹⁴,A_⊥¹⁴等张量参数。利用测得的波谱参数计算了键参数,并讨论了配合物的电子结构及成键特性,得到了较满意的结果。     

Tb3+掺杂高密度锗酸盐闪烁玻璃的发光性质

采用高温熔融法制备了Tb³⁺掺杂高密度锗酸盐玻璃。分别测试了该玻璃的透过光谱、密度、荧光光谱、荧光寿命及X射线激发发光光谱,揭示了该玻璃的物理化学性质和发光性质。透过光谱表明该玻璃具有良好的可见光透过率。高含量的Lu₂O₃和Gd₂O₃使得玻璃的密度高达6.4 g/cm³。该玻璃在377 nm光和X射线激发下发出强的绿光。544 nm发光的荧光寿命为1.325~1.836 ms。研究结果表明,Tb³⁺掺杂高密度锗酸盐玻璃是一种可用于慢速事件X射线探测器的候选闪烁材料。     

Energy spectra of neutrons emitted following muon capture in O and C

The energy spectra of neutrons emitted following muon capture in ¹⁶O and ¹²C are investigated using the continuum shell model. Nuclear wave functions, which have been shown by Ohtsubo and the author to describe the radiative pion capture reaction in the above nuclei well, are adopted. The calculated neutron energy spectra explain well the observed main peaks, at 5 MeV for ¹⁶O and 4 MeV for ¹²C, which are considered to be the giant resonances excited in the muon capture reaction. These peaks are interpreted as the 2⁻ state at 20.3 MeV for ¹⁶O and the 1⁻ state at 22.5 MeV for ¹²C. Comparisons with photon spectra in radiative pion capture reactions are also made. The calculated total capture rates exceed the experimental values by a factor of 2.5 for ¹⁶O and by 30–40% for ¹²C.     

BeC分子基态和低激发态光谱性质和解析势能函数

BeC是一个具有丰富低激发电子态的分子,本文基于动态权重完全活性空间自冾场方法获得的参考波函数,采用多参考组态相互作用方法对BeC分子进行高精度的从头计算,获得了BeC分子X~3Σ~-,A~3Π,b~1Δ,c~1Π和d~1Σ~+共5个电子态的势能曲线.为了获得精确的光谱结果,在计算中考虑了标量相对论效应修正,并把相互作用能外推至完全基组极限.在此基础上获得了这些态的光谱常数和偶极距,以及一些允许跃迁的跃迁偶极距、弗兰克-康登因子和辐射寿命.最后,通过扩展的Rydberg函数拟合获得了基态势能曲线精确的解析表达式.     

Gd2(WO4)3: Eu纳米发光材料中黄昆因子和能量传递速率的实验获得

采用共沉淀法制备了不同Eu³⁺掺杂浓度的Gd₂(WO₄)₃纳米发光材料. 测量了纳米材料样品的X射线衍射谱(XRD) 和场发射扫描电镜, 对样品的结构和形貌进行了表征. 测量了各样品的发射光谱和激发光谱(声子边带光谱), 绘制了浓度猝灭曲线, 确定了最佳的掺杂浓度为20 mol%. 通过声子边带光谱计算了不同掺杂浓度样品的黄昆因子. 测量了不同浓度样品的荧光寿命, 利用Auzel模型对Eu^{3+ 5}D₀能级荧光寿命数据进行了拟合, 确定了⁵D₀能级的固有寿命和猝灭过程中生成的声子数. 本文还根据荧光寿命数据计算了Eu³⁺之间的能量传递速率, 确定了能量传递速率与浓度的关系. 关键词： 钨酸盐 3+')" href="#">Eu³⁺ 黄昆因子 能量传递速率     

用差分收敛法研究NaLi分子部分电子态的完全振动能谱

基于双核分子振动能级的普遍表达式和差分收敛法(difference converging method, DCM), 利用微分思想将DCM应用于双核分子体系完全振动能谱的研究中. 应用DCM方法, 分别选用实验上获得的一组(10条)精确的振动能级, 对NaLi分子3¹Π, 4¹Π 和A¹Σ⁺电子态进行了研究, DCM的研究结果正确重复了已知数据并预测出了在实验上未能获得的包含高激发态在内的完全振动能谱数据, 同时计算得到了这3个电子态的振动光谱常数.     

钌(Ⅱ)配合物与DNA相互作用的瞬态发光特性

以三种新合成的钌配合物[Ru(bpy)₂(7-CH₃-dppz)]²⁺、[Ru(bpy)₂(7-F-dppz)]²⁺、[Ru(phen)₂(7-F-dppz)]²⁺为研究对象,采用时间分辨的荧光光谱技术分别测量了这三种钌配合物与小牛胸腺DNA相互作用时的瞬态荧光动力学过程。结果表明:[Ru(bpy)₂(7-CH₃-dppz)]²⁺的发光寿命最长(约382 ns),而[Ru(bpy)₂(7-F-dppz)]²⁺的发光寿命最短(约65 ns)。分析表明:钌配合物的发光来源于配合物分子中的电荷转移态到基态的辐射跃迁。通过钌配合物与DNA的相互作用,使得配合物激发态分子的无辐射弛豫几率减小,从而导致发光寿命的增加。配合物的分子与DNA相互作用越强,激发态分子的无辐射弛豫几率越小,发光寿命也越长,最终导致高的发光效率。配合物的分子结构对配合物的分子与DNA的相互作用具有重要的影响。     

MRCI+Q study of the low-lying electronic states of CdF including spin-orbit coupling

Cd F molecule, which plays an important role in a great variety of research fields, has long been subject to numerous researchers. Due to the unstable nature and heavy atom Cd containing in the Cd F molecule, electronic states of the molecule have not been well studied. In this paper, high accurate ab initio calculations on the Cd F molecule have been performed at the multi-reference configuration interaction level including Davidson correction(MRCI + Q). Adiabatic potential energy curves(PECs) of the 14 low-lying Λ–S states correlating with the two lowest dissociation limits Cd(~1S_g) + F(~2P_u) and Cd(~3P_u) + F(~2P_u) have been constructed. For the bound Λ–S and ? states, the dominant electronic configurations and spectroscopic constants are obtained,and the calculated spectroscopic constants of bound states are consistent with previous experimental results. The dipole moments(DMs) of 2 Σ+ and 2Π are determined, and the spin–orbit(SO) matrix elements between each pair of X2Σ+, 22Σ+, 12Π, and 22Π are obtained. The results indicate that the sudden changes of DMs and SO matrix elements arise from the variation of the electronic configurations around the avoided crossing region. Moreover,the Franck–Condon factors(FCFs), the transition dipole moments(TDMs), and radiative lifetimes of low-lying states-the ground state X2Σ+are determined. Finally, the transitional properties of 22Π–X2Σ+and 22Σ+–X2Σ+are studied. Based on our computed spectroscopic information of Cd F, the feasibility and challenge for laser cooling of Cd F molecule are discussed.     

Chemical effects of Ne bombardment on the MoS2(0001) surface studied by high-resolution photoelectron spectroscopy

The effect of 1 keV Ne⁺ bombardment on the clean MoS₂(0001)-1 × 1 surface with fluences between 4 × 10¹⁴ and 4 × 10¹⁶ Ne⁺/cm² was studied using high-resolution photoelectron spectroscopy excited with synchrotron radiation. Spectra of the Mo 3d and S 2p core levels were measured with photon energies that ensured that the kinetic energy of the photoelectrons was the same, resulting in the same depth being probed for both core levels. For lower fluences (i.e., 2 × 10¹⁵ Ne⁺/cm²), S vacancy defect formation occurs in the MoS₂ lattice, with the concurrent formation of a small amount (< 10%) of dispersed elemental molybdenum [Mo(0)]. For fluences greater than l × 10¹⁶ Ne⁺/cm², the Mo(0) is the predominant species in the surface region, while the remaining species consist of amorphous MoS_2−x and polysulfide species. Valence band spectra taken with photon energies of 152 and 225 eV were consistent with the core level results. The movement of the valence band maximum toward the Fermi level indicated the formation of a metallic surface region. Annealing the sample to temperatures up to 1000 K resulted in the formation of metallic Mo coexisting, in approximately equal amounts, with reformed MoS₂ in a surface with no long-range order as determined by LEED. Finally, a qualitative depth distribution of the chemical species present after Ne⁺ bombardment was determined by varying the photon energies used for the core level spectra. The results indicate that the preferential sputtering of sulfur over molybdenum occurs predominantly through a mechanism involving chemical bonding effects, specifically, through the preferential emission of polysulfide ions over other species in the bombarded region.     

掺Er3+碲酸盐玻璃的光谱性质与Judd-Ofelt理论分析

用高温熔融法制备了碲酸盐玻璃(70TeO₂-9B₂O₃-6Nb₂O₅-5Na₂O-10ZnO-1%(质量分数)Er₂O₃)样品。测试了玻璃样品的吸收光谱和荧光光谱。应用Judd-Ofelt理论计算了Er³⁺离子的谱线强度、自发辐射跃迁几率、荧光分支比、辐射寿命等光谱参数,并拟合了相应的强度参数Ω_t(t=2,4,6)(Ω₂=8.01×10^-20cm²,Ω₄=2.09×10^-20cm²,Ω₆=1.15×10^-20cm²)。结果发现该碲酸盐玻璃具有较大的Ω₂值,说明Er—O键的共价性强于它在硅酸盐、锗酸盐、氟化物、铋酸盐和磷酸盐玻璃中的共价性。Er³⁺在碲酸盐玻璃中⁴I_13/2→⁴I_15/2跃迁几率约为492s^-1,表明Er³⁺可能有较强的1.5μm发射。分析了Er³⁺在碲酸盐玻璃中能级⁴I_13/2→⁴I_15/2发射的荧光半峰全宽(FWHM=73nm),并应用McCumber理论计算了Er³⁺的受激发射截面(σ_e=1.08×10^-20cm²),发现其FWHM×σ_e远大于Er³⁺在铋酸盐、磷酸盐、锗酸盐和硅酸盐玻璃中的受激发射截面,说明碲酸盐玻璃是一种制备宽带光纤放大器的优良基质材料。     

光谱参数法快速识别石油烃污染场地水体特征

水体受石油污染日趋广泛,给人类及生态环境带来严重威胁。快速、准确和可靠地监测水体石油污染状况,对于理解其环境行为和评估人体暴露风险至关重要。石油类组分往往具备较好的光谱响应,然而基于光谱技术快速监测实际石油烃污染水体却鲜有报道。该研究以典型石油污染场地的地下水和地表水为对象,在全面分析水质电导率、总有机碳,Cl-,NO-₃,SO2-₄,Na+,K+,Mg2+,Ca2+,NH+₄,挥发性有机物和石油烃C₆-C₉,C₁₀-C₁₄,C₁₅-C₂₈,C₂₉-C₄₀浓度基础上,对水体样品进行紫外-可见光光谱、同步荧光光谱、三维荧光光谱表征,采用多元数据分析手段评估光谱技术在石油污染场地快速识别应用的可能性。结果表明：①紫外-可见光光谱和同步荧光光谱参数表明,污染的地下水中含有大量芳香族化合物,且有机物分子结构复杂,含有大量的羟基、羰基、羧基和酯类等取代基,三维荧光光谱参数表明污染水体中有机物经过了长时间的生物转化,说明污染地下水中有机物稳定性强,降解性差;②三维荧光光谱图表现出Ⅰ和Ⅳ区明显的荧光峰,Ⅴ区存在肩峰的水体主要是苯系物污染,而三维荧光光谱图表现出Ⅱ和Ⅳ区明显的荧光峰,Ⅰ区存在肩峰的水体主要是萘系物污染,三维荧光光谱图表现出Ⅱ区最高荧光峰,Ⅰ,Ⅲ,Ⅳ和Ⅴ都存在肩峰的水体主要是萘系物和菲系物污染;③石油烃C₆-C₉组分浓度可采用紫外-可见光光谱参数S_308～363,SUVA₂₅₄和三维荧光光谱中Ⅰ区体积快速指示,石油烃C₁₀-C₁₄组分和总石油烃（TPH）浓度可采用三维荧光光谱中Ⅳ区体积快速指示,石油烃C₁₅-C₂₈和C₂₉-C₄₀组分浓度可采用三维荧光光谱中Ⅰ区体积快速指示。研究证实利用光谱参数结合多元数据分析可对石油污染水体进行快速识别,为地下水石油污染监测和修复提供了一种全新的快速在线监测分析方法。     

Solid-state 17O NMR study of the electric-field-gradient and chemical shielding tensors in polycrystalline gamma-glycine

We report the first experimental determination of the carboxylate oxygen electric-field-gradient (EFG) and chemical shielding (CS) tensors in polycrystalline γ-glycine. Analysis of magic-angle spinning (MAS) and stationary ¹⁷O NMR spectra of [¹⁷O]-γ-glycine obtained at 9.4, 14.1, 16.4, and 18.8 T yields the magnitudes of the ¹⁷O EFG and CS tensors and the relative orientations between the two tensors. Extensive quantum chemical calculations at both the restricted Hartree–Fock and density functional levels have been performed to present the absolute tensor orientations in term of the molecular frame. We have demonstrated that ¹⁷O NMR tensor information could be unambiguously derived by the multiple field analyses of stationary ¹⁷O NMR spectra.     

Investigation of 1.3 μm emission in Nd-doped bismuth-based oxide glasses

Nd₂O₃-doped 43Bi₂O₃–xB₂O₃–(57−x)SiO₂–1.0Nd₂O₃ (x=57, 47, 39, 28.5, 19.5, 10, 0 mol%) bismuth glasses were prepared by the conventional melt-quenching method, and the Nd³⁺: ⁴F_3/2→⁴I_13/2 fluorescence properties had been studied in an oxide system Bi₂O₃–B₂O₃–SiO₂. The Judd–Ofelt analysis for Nd³⁺ ions in bismuth boron silicate glasses was also performed on the basis of absorption spectrum, and the transition probabilities, excited-state lifetimes, the fluorescence branching ratios, quantum efficiency and the stimulated emission cross-sections of ⁴F_3/2→⁴I_13/2 transition were calculated and discussed. The stimulated emission cross-sections of 1.3 μm were quite large due to a large refractive index of the host. Although the effective bandwidths decreased with increasing SiO₂ content, quantum efficiencies and stimulated emission cross-sections enhanced largely with increasing SiO₂ content.