PbWO4晶体电子结构的理论计算

采用相对论性的离散变分DV-Xα方法模拟计算了具有复杂晶体结构的PbWO₄晶体的本征能级结构,其价带顶主要由O 2p轨道组成,导带底主要由W 5d轨道构成;Pb 6s电子的绝大部分分布在距价带底～2eV处的窄带中,同时也有少量分布在价带;禁带宽度大约是4.4eV,计算结果与实验数据符合得较好. 关键词：     

光纤共振拉曼光谱法痕量分析研究

在液芯光纤内产生共振拉曼效应,可以提高拉曼光谱强度１０＾９倍。样品（被测物）的浓度、模吸收系数、光散射系数和模耦合系数决定光纤最佳长度。该技术分子光谱研究提供了一种新实验方法,在痕量分析、液体中少量分子相互作用研究等方面有很大的应用潜力。低浓度的β－胡萝卜素（β－ｃａｒｏｔｅｎｅ）在ＣＳ２中和Ｉ２在ＣＳ２中的拉曼光谱被得到,其浓度分别是１×１０＾－１３ｍｏｌ／Ｌ和１×１０＾－１４ｍｏｌ／Ｌ。     

原子吸收光谱测定刺五加中金属元素的含量

用原子吸收光谱法测定了刺五加根、茎、叶中Ca、Cu、Mg、Fe、Zn、K、Mn、Na等8种矿物质元素的含量,并对其结果进行了分析比较,以此研究了这8种金属元素在刺五加体内的分布。结果显示：各元素在实验范围内,线性关系良好,加标回收率在99%—109.6%之间,相对标准偏差为0.2%—1.8%。刺五加中不同部位的这8种元素间存在显著差异,根中Ca〉Mg〉K〉Fe〉Na〉Mn〉Zn〉Cu,其叶中的含量以K为高,而且各部位均有较高的Ca、Cu、Mg、Fe、Zn、K、Mn、Na。从微量元素的角度分析,刺五加的根、茎、叶均有一定的应用价值。     

Excitonic Coupling between B and Q Transitions in Porphyrin Aggregates

The properties of meso-tetraphenylporphine （TPP） aggregates formed in acidic aqueous-organic solutions are investigated by UV-vis spectroscopy. According to the absorption spectra, the Q band absorption of the aggregated TPP shows red shift and intensity enhancement, and a model that includes the participation of water molecules in a porphyrin aggregation complex is proposed, then a qualitative explanation based on Gouterman＇s excition coupling theory is presented. Calculations including eigenenergies, eigenstates and the transition dipole strength of the coupled states are carried out.     

CS2中对苯醌n-π*单-三态跃迁的可见吸收光谱及其共振拉曼光谱

测量了对苯醌(p-benzoquinone,PBQ)在CS2中的可见吸收光谱,论证了该实验中发现的507 nm带来源于PBQ的n-π*单-三态跃迁.基于液芯光纤内共振拉曼散射可以提高拉曼光谱强度109倍这一技术,在10-3～10-6 mol·L-1的浓度范围首次探测到514.5 nm激光激发该跃迁而产生的共振拉曼光谱(1 439cm-1).分析认为该谱线来源于PBQ的n-π*单-三态跃迁的羰基伸缩振动(v c-o).实验发现,随着PBQ溶液浓度的降低,该谱线的拉曼频移发生蓝移.文章的研究结果将有助于理解PBQ电子结构与其光物理特性的相互关系,便于获得更丰富的分子结构信息.     

液芯光纤光谱仪

液芯光纤可以使拉曼光谱强度提高103倍。将液芯光纤既作为样品池又作为前置放大系统,研制成功了体积小、重量轻、成本低、灵敏度高的小型拉曼光谱仪。结果表明:通过对液体及溶在液体中的样品进行自发拉曼光谱、共振拉曼光谱的测量,获得了理想的拉曼光谱。     

The effect of anti-hydrogen bond on Fermi resonance: A Raman spectroscopic study of the Fermi doublet ν1—ν12 of liquid pyridine

The effects of anti-hydrogen bond on the ν₁—ν₁₂ Fermi resonance (FR) of pyridine are experimentally investigated by using Raman scattering spectroscopy. Three systems, pyridine/water, pyridine/formamide, pyridine/carbon tetrachloride, provide varying degrees of strength for the diluent-pyridine anti-hydrogen bond complex. Water forms a stronger anti-hydrogen bond with pyridine than with formamide, and in the case of adding non-polar solvent carbon tetrachloride, which is neither a hydrogen bond donor nor an acceptor and incapable of forming hydrogen bond with pyridine, the intermolecular distance of pyridine will increase and the interaction of pyridine molecules will reduce. The dilution studies are performed on the three systems. Comparing with the values of Fermi coupling coefficient W of the ring breathing mode ν ₁ and triangle mode ν ₁₂ of pyridine at different volume concentrations, which are calculated according to the Bertran equations, in three systems, we find that the solution with the strongest anti-hydrogen bond, water, shows the fastest change in the ν₁—ν₁₂ Fermi coupling coefficient W with the volume concentration varying, followed by the formamide and carbon tetrachloride solutions. These results suggest that the stronger anti-hydrogen bond-forming effect will cause a greater reduction in the strength of the ν₁—ν₁₂ FR of pyridine. According to the mechanism of the formation of anti-hydrogen bond in the complexes and the FR theory, a qualitative explanation for the anti-hydrogen bond effect in reducing the strength of the ν₁—ν₁₂ FR of pyridine is given.     

外场对π电子能隙调制C==C，C-C伸缩振动的影响

共振拉曼光谱是研究线性多烯分子的主要分子光谱技术。该技术完美地表征了π电子能隙对C==C,C-C伸缩振动的调制规律。这种调制是通过电子-声子耦合完成的。改变外界环境,能隙调制作用将受到影响。测量了溶剂中β-胡萝卜素分子在温度、压力、溶剂效应、相变等不同环境影响下的吸收光谱、共振拉曼光谱,研究了不同外场对π电子能隙调制C==C,C-C伸缩振动的影响机理及规律。结果表明,在外场影响下,体系的能量降低,π电子能隙(π-π*)减小会使调制增强。即电子-声子耦合增强,使拉曼强度增加,谱线红移。对理解共振拉曼物理过程,认识线性多烯分子的结构,性能有重要意义,对研制优质光电器件也有参考价值。     

火炮立楔式炮闩抽筒系统的动态特性

针对火炮立楔式炮闩抽筒系统中的卡壳和构件动态断裂等抽筒故障,以动力学理论为基础,将其转化为系统动态特性的定量研究。分析了抽筒系统的工作机理并建立了连续接触动力学模型,定量地推导出药筒及系统内接触构件的运动规律和碰撞载荷。建立了杠杆式抽筒子在抽筒过程中的弹性波动模型,采用该模型能够定量地得出抽筒子的动应力分布和力学参数的影响。进行了理想抽筒工况下理论模型的数值计算和实体模型的仿真模拟,同组比较结果验证了定量分析模型的合理性。所建模型可为解决抽筒故障提供理论依据,也可为抽筒系统的动力学和结构优化设计作铺垫。