Electronic Structure of Alkali Metal Sulfates

A calculation of the band structure, state density, valence and difference densities of Na₂SO₄, LiKSO₄, NaKSO₄ is carried out within the framework of the theory of local electron density by the pseudo-potential method based on numerical sp ³ d ⁵- pseudo-orbitals. The absorption edge of these crystals is found to be circuitous. The partial composition of the valence band is analyzed, and the contribution from non-equivalent oxygen atoms in individual sub-bands is revealed to be different. The band structure of LiKSO₄ is shown to essentially differ from that of Na₂SO₄ and NaKSO₄ in the number of isolated band bunches and state density structure. It is shown that the polarizing effects of cations on anions gives rise to considerable changes in electric charge distribution, which, in particular, results in the formation of a tetrahedral complex LiO₄.     

掺杂碱金属与碱土金属的CuO-CeO_2催化剂的漫反射红外光谱分析

CuO-CeO2系列催化剂是高效的CO选择性氧化反应的催化剂,通过原位漫反射红外光谱对掺杂碱金属和碱土金属氧化物的CuO-CeO2催化剂表面的吸附物种进行了研究。结果表明CuO-CeO2系列催化剂上,2 106 cm-1处出现CO的红外吸附峰。在反应气氛中,此峰的强度随着温度先升高后降低,说明Cu+是CO主要的活性吸附中心。低温下催化剂表面吸附的CO主要以可逆形式脱附出来,而高温下CO则以不可逆的形式脱附出来。催化剂表面在3 660 cm-1处出现尖锐的红外峰,归属于CeO2经还原产生的Ce-(OH)2偕式基团。在1 568,2 838和2 948 cm-1附近处出现甲酸根的红外谱峰,以及1 257和1 633 cm-1处出现碳酸根物种的红外峰。甲酸根物种是气相的CO与表面的羟基反应生成的产物,该物种的C—H键断裂生成碳酸根物种,这两物种均会降低催化剂的高温活性。Cu1Li1Ce9Oδ催化剂出现较强的CO2和甲酸根的红外峰,温度高于180℃时,该催化剂上还能看到微弱的CO红外峰,说明锂离子的给电子性质有利于提高Cu1Li1Ce9Oδ催化剂上CO的不可逆脱附,抑制氢的活化吸附,同时促进了甲酸根物种的生成。低温下Cu1Mg1Ce9Oδ和Cu1Ba1Ce9Oδ催化剂上CO的吸附量较多,但主要以可逆脱附形式脱附出来,对CO选择性氧化没有贡献。     

The Fine Structure of Alkali Metal Atoms in Inelastic Collisions with Hydrogen

Optics and Spectroscopy - A method is proposed for calculating the rate constants of inelastic processes occurring during collisions of alkali metal atoms and their positive ions with hydrogen...     

二元碱金属硅酸盐精细结构和拉曼光谱的从头计算研究

应用量子化学从头计算方法研究了二元碱金属硅酸盐的精细结构,对典型的系列二元碱金属硅酸盐离子簇模型采用6-31G(d)基组和闭壳层Hartree-Fock(RHF)方法优化构型,并计算了二元碱金属硅酸盐的拉曼光谱,采用硅氧四面体应力指数这一精细结构参数分析和讨论了计算得到的非桥氧高频区对称伸缩振动频率和其拉曼光学活性,以及不同阳离子对该拉曼光学活性的影响。研究表明,二元碱金属硅酸盐非桥氧高频区对称伸缩振动频率与其精细结构密切相关,而且与Q₃相连的Q₄会对该Q₃的拉曼光学活性表现出增强作用。这说明二元碱金属硅酸盐的拉曼散射等性质主要依赖于其精细结构而非其初级结构单元-硅氧四面体。研究还表明,半径较大的阳离子有利于增强离子簇的拉曼光学活性,但对于小的离子簇,过多的电荷迁移反而会起到抑制作用。     

Electronic Properties of a Two-Dimensional Electron Gas at the Interface between Transition Metal Complex Oxides

The structural and electronic properties of heterostructures based on transition metal oxides containing strongly correlated electrons are compared. The investigated structures are LaAlO₃/SrTiO₃ (LAO/STO), LaAlO₃/BaTiO₃ (LAO/BTO), and BaTiO₃/SrTiO₃ (BTO/STO). The role of structural relaxation in the formation of a two-dimensional electron gas at the interface of two dielectrics is revealed. The contribution from different orbitals and atoms to conductivity is analyzed, along with the correlation between structural distortions induced by the dipole moment in an LAO layer and conductivity.     

碱金属改性的纳米氧化锌基荧光材料

研究了Zn （NO3）2·6H2O、CO （NH2）2、R-C6H4-SO3Na、Eu2O3和LiNO3为原料,通过均匀沉淀法制备了Eu3＋、Li＋共掺杂的纳米ZnO材料,并通过改变Li＋的掺杂比例来研究纳米氧化锌基材料的发光性能,用XRD、紫外和荧光等分析手段对样品进行表征.结果表明：制得的纳米粉体粒径在50nm左右,引入Li＋后增强了纳米ZnO∶Eu3＋材料的紫外可见光吸收和红色发光性能,且与Li＋的掺杂浓度有关,当Li＋∶Eu3＋的摩尔比为0.6时,其在601nm处的特征峰最强.     

Laser Raman Spectra of Transition Metal Oxides and Catalysts

Abstract

During recent years the study of the vibrational structure of catalysts by laser Raman spectroscopy (LRS) and of the interfacial properties of adsorbed species on solid surfaces by resonance Raman spectroscopy (RRS) and surface-enhanced Raman spectroscopy (SERS) have comprised one of the major research activities in the area of Raman spectroscopy [1–10] as applied to catalysts [11, 12].     

Composition and Thermodynamic Properties of Dense Alkali Metal Plasmas

In this work composition and thermodynamic properties of dense alkali metal plasmas (Li, Na) were investigated. Composition was derived by solving the Saha equations with corrections due to nonideality. The lowering of the ionization potentials was calculated on the basis of pseudopotentials by taking screening and quantum effects into account (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

钛氧化物结构及其拉曼光谱表征

采用密度泛函理论(DFT),对几种钛的氧化物晶体结构进行了几何构型优化,得到了与X-ray晶体衍射实验结果相一致的结构参数。在优化几何构型基础上进行了分子振动模的分析和计算,钛氧化物均采用数字化基组和局域密度近似,并选择vwn对局域交换相关能量参数化,使用自旋非限制函数。同时,测定了钛的氧化物(TiO, Ti₂O₃,Ti₃O₅,锐钛矿型TiO₂和金红石型TiO₂)几种晶体的拉曼光谱,并分别解释了相关的拉曼活性振动模。结果表明：计算的频率与实验结果比较一致,理论计算频率可以指导实验谱图谱峰位置的归属分析。通过钛的一系列氧化物的常温拉曼光谱分析, 得知不同氧化物有不同特征峰,有利于含钛氧化物材料类型的诊断,为沟通结构和性能的相互关系奠定基础。     

化合物/银核壳结构纳米复合颗粒的消光性能研究

利用离散偶极近似(Discrete Dipole Approximation,DDA)方法系统研究ITO/Ag、CdS/Ag、和ZnS/Ag纳米核壳结构的消光特性。研究结果表明,银纳米核壳的表面等离子体共振吸收峰位置随周围介质折射率和颗粒核壳比的增大逐渐红移;且当核壳比相同时,较大球径纳米核壳的消光峰位置处在长波长处。研究亦发现,银壳与化合物之间存在显著的电子迁移现象,相同球径的银表面电子密度降低程度由高到低为CdS/Ag、ZnS/Ag、ITO/Ag。     

Energy Band Genesis from Sublattice States in Sulfides of Alkali Metals with an Antifluorite Lattice

Based on the density functional, self-consistent band spectra from crystals and charged sublattices of alkali metal sulfides are calculated by the method of pseudopotential in the basis of localized orbitals. Different charge states of sublattices compatible with the electric neutrality of crystals are addressed, including extrememost states: neutral sublattices, and unfilled metal and double charged anionic sublattices. It is shown that a transfer of fractional charges by the anionic sublattices results in a reasonable recovery of parameters of the valence bands of crystals. The lower conduction bands for this charge distribution are similar in crystals and fractionally charged anionic sublattices. The differences found out are accounted for by sublattice hybridization.__________Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 30–34, February, 2005.     

Strongest Magnetically Induced Transitions in Alkali Metal Atoms

JETP Letters - Atomic transitions in alkali metals that have zero probability in the absence of a magnetic field but have large probabilities in the presence of a magnetic field are called...     

富勒烯C32分子器件结构和传导特性的理论研究

利用基于第一性原理的密度泛函理论(DFT)和非平衡格林函数(NEGF)方法对富勒烯C32分子及在C32的距离最远的两个碳原子处外接Li电极的C32分子器件进行了电子结构、电子传输性质的研究。设计了C32笼内嵌入Mg原子,外接Li电极的分子器件。通过计算,得出了两个分子器件的电子传输谱,分析了他们的电子结构和电子输运特性。说明了C32分子器件的电子传输主要集中于C32分子的壳表上,并且分子球的内侧和外侧的电子传输相近似。在C32分子内部嵌入Mg原子后,分子器件的电子传输仍主要集中在分子表面上,但在系统Mg@C32中,表面内侧的电子传输要比表面外侧的电子传输强。通过比较,结果表明两种富勒烯分子的电子传输性能顺序为Mg@C32>C32。     

C50富勒烯分子的电子结构与传输特性研究

本文构建了Au原子面为电极的富勒烯C50分子的电子输运模型, 使用非平衡格林函数方法(Non-equilibrium Green's function, NEGF)对构建的Au电极和C50分子构成的分子器件进行了电子传输性质的计算. 通过计算得出了电子透射谱、电导曲线和电流电压曲线, 分析了产生这个分子器件电子输运性质的原因. 研究计算结果发现：C50分子具有量子器件的开关特性,并具有明显的半导体特征.     

碱金属碱土金属化合物标准熵的拓扑研究

定义离子极化力参数 gi.在分子拓扑图的邻接矩阵基础上 ,由 gi 建构极化力连接性指数 mG ,其中 0 G、1G对无机分子有良好的结构选择性 .计算了 6 4种碱金属、碱土金属的氧化物、卤化物、硫化物、硒化物等的 0 G、1G ,发现它们的标准熵与分子的大小及分子中的原子数正相关 ,而与分子中离子的极化力负相关 .这与其标准熵的递变规律相一致 .所以 ,化合物的 0 G、1G必然与其标准熵表现出良好的相关性 .研究结果表明 ,其预测值和实验值基本吻合 ,优于Latimer法以及Randic Kier连接性指数     

EPR of Charge Carriers Stabilized at the Surface of Metal Oxides

Some cases of formation and stabilization of charge carriers (electron and holes) at the surface of solid oxides are discussed. Charge carriers can be simultaneously or independently stabilized at the surface metal oxides. In the former case, they usually derive from a process of charge separation in the solid triggered by above band gap irradiation. In the second case, the charge carrier isolation is the result of a chemical alteration of the stoichiometric equilibrium of the solid either by matter addition or by effect of chemical impurities (valence induction). Electron paramagnetic resonance (EPR) is highly suited to monitor the process of charge separation and to characterize electron or hole centers stabilized in the solid or at its surface. In this paper examples of trapped electron and/or trapped hole centers as detected by continuous-wave EPR at the surface of simple binary oxides are discussed with particular emphasis to the formation mechanism, the EPR parameters and the chemical reactivity.     

镎氧化物分子结构和光谱的理论研究

运用密度泛函理论(DFT)的B3LYP方法,优化了NpO,NpO_2,NpO_3和Np_2O_3分子的几何构型,分析了电子从Np到O的转移情况。结果表明:NpO,NpO_2,NpO_3和Np_2O_3的自旋多重度分别为6,2,2和9,对称性分别为C_(∞v),D_(∞h),C_(2v)和D_(3h)时相应分子处于稳定结构;对所有分子而言,分子能级在-50 eV左右的态主要由Np-6s轨道形成,在-20 eV附近的态主要由Np-6p和O-2s轨道混合组成,而大于-11 eV的态主要由Np-5f和O-2p轨道混合组成。同时,根据相关计算给出了分子基态结构的振动频率和光谱数据,并对红外光谱最大峰值的振动模式进行了指认。