Extraction of local coordination structure in a low‐concentration uranyl system by XANES

Obtaining structural information of uranyl species at an atomic/molecular scale is a critical step to control and predict their physical and chemical properties. To obtain such information, experimental and theoretical L₃‐edge X‐ray absorption near‐edge structure (XANES) spectra of uranium were studied systematically for uranyl complexes. It was demonstrated that the bond lengths (R) in the uranyl species and relative energy positions (ΔE) of the XANES were determined as follows: ΔE₁ = 168.3/R(U—O_ax)² ? 38.5 (for the axial plane) and ΔE₂ = 428.4/R(U—O_eq)² ? 37.1 (for the equatorial plane). These formulae could be used to directly extract the distances between the uranium absorber and oxygen ligand atoms in the axial and equatorial planes of uranyl ions based on the U L₃‐edge XANES experimental data. In addition, the relative weights were estimated for each configuration derived from the water molecule and nitrate ligand based on the obtained average equatorial coordination bond lengths in a series of uranyl nitrate complexes with progressively varied nitrate concentrations. Results obtained from XANES analysis were identical to that from extended X‐ray absorption fine‐structure (EXAFS) analysis. XANES analysis is applicable to ubiquitous uranyl–ligand complexes, such as the uranyl–carbonate complex. Most importantly, the XANES research method could be extended to low‐concentration uranyl systems, as indicated by the results of the uranyl–amidoximate complex (～40 p.p.m. uranium). Quantitative XANES analysis, a reliable and straightforward method, provides a simplified approach applied to the structural chemistry of actinides.     

The effect of self‐consistent potentials on EXAFS analysis

A theory program intended for use with extended X‐ray‐absorption fine structure (EXAFS) spectroscopy and based on the popular FEFF8 is presented. It provides an application programming interface designed to make it easy to integrate high‐quality theory into EXAFS analysis software. This new code is then used to examine the impact of self‐consistent scattering potentials on EXAFS data analysis by methodical testing of theoretical fitting standards against a curated suite of measured EXAFS data. For each data set, the results of a fit are compared using a well characterized structural model and theoretical fitting standards computed both with and without self‐consistent potentials. It is demonstrated that the use of self‐consistent potentials has scant impact on the results of the EXAFS analysis.     

Path degeneracy and EXAFS analysis of disordered materials

Analysis of EXAFS data measured on a material with a disordered local configuration environment around the absorbing atom can be challenging owing to the proliferation of photoelectron scattering paths that must be considered in the analysis. In the case where the absorbing atom exists in multiple inequivalent sites, the problem is compounded by having to consider each site separately. A method is proposed for automating the calculation of theory for inequivalent sites, then averaging the contributions from sufficiently similar scattering paths. With this approach, the complexity of implementing a successful fitting model on a highly disordered sample is reduced. As an example, an analysis of Ti K‐edge data on zirconolite, CaZrTi₂O₇, which has three inequivalent Ti sites, is presented.     

Electronic structures and vibrational properties of coronene on Ru(0001): first-principles study

We calculate the configurations, electronic structures, vibrational properties at the coronene/Ru(0001) interface, and adsorption of a single Pt atom on coronene/Ru(0001) based on density functional theory calculations. The geometric structures and electronic structures of the coronene on Ru(0001) are compared with those of the graphene/Ru(0001). The results show that the coronene/Ru(0001) can be a simplified model system used to describe the interaction between graphene and ruthenium. Further calculations of the vibrational properties of coronene molecule adsorbed on Ru(0001) suggest that the phonon properties of differently corrugated regions of graphene on Ru(0001) are different. This model system is also used to investigate the selective adsorption of Pt atoms on graphene/Ru(0001). The configurations of Pt on coronene/Ru(0001) with the lowest binding energy give clues to explain the experimental observation that a Pt cluster selectively adsorbs on the second highest regions of graphene/Ru(0001). This work provides a simple model for understanding the adsorption properties and vibrational properties of graphene on Ru(0001) substrate.     

Crystal growth,spectral properties and Judd–Ofelt analysis of Pr: CaF_2-YF_3

The 0.6 at.% Pr~(3+)-doped CaF_2-YF_3 crystal was successfully grown by the temperature gradient technique(TGT).X-ray diffraction analysis showed that the grown crystal still had cubic structure. The absorption spectrum, emission spectrum, Judd–Ofelt analysis and fluorescence decay curve at room temperature were discussed. The fluorescence lifetime of Pr: CaF_2-YF_3 crystal was 45.46 μs, and the σem ·τ of ~3P_0→~3H_6 and ~3P_0→~3F_2 transitions were calculated to be 80.92 × 10~(-20) cm~2·μs and 388.7 × 10~(-20) cm~2·μs, respectively. The FWHMs are 20.1 nm and 6.8 nm, which are higher than those of Pr: LiYF_4, Pr:LiLuF_4, Pr: LiGdF_4 and Pr: BaY_2F_8 crystals. The results show that the Pr: CaF_2-YF_3 crystal is expected to achieve 605 nm orange light and 642 nm red light laser operation.     

稀土钇、镧掺杂TiO2薄膜的拉曼谱分析

采用溶胶-凝胶法在石英玻璃衬底上用旋涂法制备了未掺杂、掺杂钇和掺杂镧的TiO₂薄膜样品,对样品在700—1100 ℃范围内进行退火处理,并对样品的拉曼光谱进行了分析.分析表明:随着退火温度的升高,未掺杂TiO₂薄膜发生了从锐钛矿相经混相最终向金红石相的转换,掺杂钇和掺杂镧对TiO₂薄膜的晶相转换起阻碍作用,掺杂镧的阻碍作用更强;稀土掺杂能使TiO₂薄膜晶粒细化,并使晶粒内部应力增大从而阻碍晶格振动,掺杂镧比掺杂钇的效果 关键词： 2薄膜')" href="#">TiO₂薄膜 稀土掺杂 拉曼光谱 溶胶-凝胶     

高功率固体激光装置光学元件“缺陷”分布的功率谱密度方法及等效求法

提出采用功率谱密度（PSD）的方法来描述光学元件的“缺陷”分布状况.以数目巨大的微米量级振幅调制型缺陷为例,基于统计思想,得到了光学元件“缺陷”分布等效PSD的求法,并验证了等效求法的合理性. 关键词： 功率谱密度 统计分析 等效求法 “缺陷”     

Charge‐dependent adsorption of rhodamine 6G on gold nanoparticle surfaces: fluorescence and Raman study

We study the adsorption behaviors of rhodamine dyes on gold nanoparticles (Au NPs) depending on their surface charges. Rhodamine 6G (Rh6G) dye is tested comparatively for positively and negatively charged Au NPs prepared by the reduction of chitosan and citric acid, respectively. The adsorption of Rh6G is found to be weaker on the positively charged Au NPs, whereas more substantial aggregation is found on negatively charged Au NPs. An increase in the concentration of Au NPs enhances the surface‐enhanced Raman scattering (SERS) intensities only for the Au(−) NPs, whereas the Au(+) NPs do not exhibit any strong SERS signals. Our findings suggest that SERS and reciprocal fluorescence measurements of Rh6G can be used to estimate the surface charges and atomic percentages of Au NPs less than ∼5 ppm. Copyright © 2011 John Wiley & Sons, Ltd.     

A DFT study of CO adsorbed on clean and hydroxylated anatase TiO2 (001) surfaces

The adsorbate–substrate interaction between carbon monoxide and clean and hydroxylated surfaces of anatase (001) was simulated by periodic DFT calculations. For the clean surface, different periodicities were taken into account in order to investigate the influence of lateral effects. The results show that the molecule interacts only with the penta-coordinated titanium ion when high surface coverages are employed, whereas it interacts with both the titanium and the di-coordinated oxygen ions when the smallest surface coverage is considered. Adsorption on the hydroxylated surface, which was carried out for the first time, was studied by considering the largest used periodicity and focusing attention on the influence of both the terminal and bridging OH groups. The resulting data show that, in the case of adsorption on the hydroxylated surface, no additional bond between the surface oxygen and the carbon atom is present. Therefore, in a regime of very low surface coverage, the molecule behaves in a very different way when it interacts with a clean or a hydroxylated surface.     

Theoretical study on adsorption properties of methyl methacrylate and its molecular chain within metal‐organic frameworks

Utilizing metal‐organic frameworks (MOFs) as a “polymerization container” is a very effective method to prepare oriented and therefore birefringent polymer materials. In particular, the adsorption of polymer monomers and molecular chains within MOFs has a profound impact on the orientation of polymer chains. In this work, a theoretical study on the adsorption properties of methyl methacrylate (MMA) and its molecular chain within MOFs has been conducted by employing a combination of molecular dynamics, density functional theory, and Monte Carlo method, where 2 MOFs, [Zn₂(1,4‐benzenedicarboxylate)₂triethylenediamine]_n and [Zn₂(4,4′‐biphenyldicarboxylate)₂triethylenediamine]_n, were chosen. The corresponding number and degree of orientation of adsorbed molecules in these 2 MOFs were obtained from the simulations. The calculation results revealed 3 factors that affect the adsorption and orientation of MMA monomers in MOF pore channels. First, as the walls of the MOF pores are polar surfaces and consist of metal ions and organic ligands, the electrostatic interaction between the MOF channels and polar MMA molecules promotes the adsorption and orientation of the MMA monomers within the pore channel. Second, the electrostatic interactions between monomers can reduce the intermolecular gaps, which similarly assist in their orientation. Last, the relative sizes of the MOF pores and the monomers are also relevant. When the sizes of the MOF channels and monomers are similar, the molecular chains show a higher degree of orientation. The results and the findings of this work could provide predictive methods for selecting polymeric monomers or MOFs that may be ideal for the control of polymer chain orientation.     

Demonstration of temperature resilient properties of 2D silicon carbide photonic crystal structures and cavity modes

In this paper, photonic crystal (PhC) based on two dimensional (2D) square and hexagonal lattice periodic arrays of Silicon Carbide (SiC) rods in air structure have been investigated using plane wave expansion (PWE) method. The PhC designs have been optimized for telecommunication wavelength (λ = 1.55 μm) by varying the radius of the rods and lattice constant. The result obtained shows that a photonic band gap (PBG) exists for TE-mode propagation. First, the effect of temperature on the width of the photonic band gap in the 2D SiC PhC structure has been investigated and compared with Silicon (Si) PhC. Further, a cavity has been created in the proposed SiC PhC and carried out temperature resiliency study of the defect modes. The dispersion relation for the TE mode of a point defect A1 cavity for both SiC and Si PhC has been plotted. Quality factor (Q) for both these structures have been calculated using finite difference time domain (FDTD) method and found a maximum Q value of 224 for SiC and 213 for Si PhC cavity structures. These analyses are important for fabricating novel PhC cavity designs that may find application in temperature resilient devices.     

Yb3+掺杂KY(WO4)2激光晶体生长、结构与光谱分析

采用顶部籽晶提拉法(TSSG)生长出Yb:KY(WO₄)₂(Yb:KYW)激光晶体.对预烧后的原料及晶体进行了XRD分析，结果表明，分别在920℃和600℃预烧8h后的熔质和助熔剂基本上形成一相，抑止了实验中的挥发问题；所生长的晶体为β-Yb:KYW，计算其晶格常数为a=1.063nm，b=1.034nm，c=0.755nm，β=130.75°.测得不同厚度样品的吸收光谱，结果表明样品在933nm和981nm有较强的吸收峰，计算出主峰981nm的吸收截面σ关键词： Yb:KYW TSSG法 晶体结构 光谱参数     

Cu(100)表面c(2×2)-N原子结构与吸附行为研究

用密度泛函理论的总能计算研究了金属铜(100)面的表面原子结构以及氮原子的c(2×2)吸附状态.研究结果表明：在Cu(100) c(2×2)-N表面系统中，氮原子处于四度配位的空洞(FFH)位置，距离最表面铜原子层的垂直距离为0.20?，最短的Cu—N键长度为1.83?.结构优化的计算否定了被吸附物导致的表面再构模型，即c(2×2)元胞的两个铜原子在垂直于表面方向发生相对位移，一个铜原子运动到氮原子之上的模型.该吸附表面的功函数约为4.65eV, 氮原子的平均吸附能为4.92 eV(以孤立氮原子为能量参考点).计算结果还说明，Cu—N杂化形成的表面局域态的位置在费米面以下约1.0 eV附近出现，氮原子和第一层以及第二层铜原子均有不同程度的杂化作用.该结果为最近有关该表面的STM图像的争论提供了判据性的第一性原理计算结果. 关键词： Cu(100) c(2×2)-N 表面吸附态 密度泛函总能计算     

First-principle study on the structural and electronic properties of H2S and SO2 adsorption on Pd-doped MoS2 monolayer

The partial discharge in SF₆-insulated equipment produces characteristic decomposition products: SO₂ and H₂S. The characteristic decomposition products vastly speed up the process of discharge faults. Based on density functional theory (DFT) calculation, single layer Pd-doped MoS₂ (Pd-MoS₂) is adopted as the adsorbent to adsorb SO₂ and H₂S to ensure the operational stability of SF₆-insulated equipment. The adsorption energy, charge transfer and structure parameters of SF₆, H₂S, and SO₂ adsorption on the Pd-MoS₂ monolayer are analysed to find the most stable adsorption structure. The molecular orbital theory, total density of states and partial density of states are studied to analyse the adsorption mechanism. The results show that Pd-MoS₂ adsorbent possesses high catalytic activity and excellent adsorption performance to H₂S and SO₂ by strong chemical adsorption. This study is of great significance to ensure the operational stability of SF6-insulated equipment by removing these characteristic decomposition products.     

Raman spectral detection and assessment of thin organic layers on metal substrates: systematic approach from substrate preparation to map evaluation

Raman spectral mapping of thin organic layers on metal substrates is an important analytical tool to characterize these systems. Surface‐enhanced Raman scattering (SERS) spectroscopy is a suitable technique for analysis of such layers. Development of new SERS‐active surfaces with repeatable properties and without disturbing adsorbed species is one of the important steps for reliable assessment of the thin organic layers designed. This paper presents new SERS‐active substrates suitable for both macro (millimeter scale) and microscopic (micrometer scale) spectral mapping, which allow easy regeneration for repetitive experiments. Both gold and silver SERS‐active surfaces prepared by electrochemical deposition were tested. Complete map data evaluation utilities were newly designed and applied, using both ordinarily used and newly modified mathematical algorithms and chemometric procedures. Evaluation of data starts with finite impulse response (FIR) filtration algorithms to eliminate spectral interferences in individual spectra. Principal component analysis was used for transformation of multidimensional data to understandable dimensions. Various mathematical/statistical techniques were then used for data visualization as spectral maps and for similarity testing. Copyright © 2008 John Wiley & Sons, Ltd.     

Effect of lattice strain on the oxygen vacancy formation and hydrogen adsorption at CeO2(111) surface

Using first-principles calculation, the effect of lattice strain on the oxygen vacancy formation at CeO₂(111) surface has been investigated. The tensile strain facilitates the oxygen vacancy formation at the surface and the compressive strain hinders the process. This is in part due to the strengthening or weakening of the surface Ce–O bond under the lattice strain. On the other hand, a more open surface with a larger lattice constant can better accommodate the larger Ce³⁺ and thus facilitate the structural relaxation of the reduced surface. The studies on the strain effect on the atomic hydrogen adsorption at the defect-free CeO₂(111) surface show that the adsorption strength monotonously increases with the increase of the lattice strain, further confirming the tunable surface chemical activity by lattice strain.     

Effects of B and N dopings and H2O adsorption on structural stability and field emission properties of cone-capped carbon nanotubes

The effects of B and N dopings and H₂O adsorption on the structural stability and the field emission properties of cone-capped carbon nanotubes (CCCNTs) were investigated by using the density-functional theoretical calculation. The adsorption of H₂O can increase the structural stability and decrease the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO gap) of the CCCNTs. The strength of total electric field on the top of the H₂O-adsorbed CCCNTs is larger than that of the B-doped and the N-doped CCCNTs, electrons will be emitted primarily from the H₂O-adsorbed CCCNTs at the same applied voltage. Therefore, the H₂O adsorption can lower the threshold voltage for the CCCNTs. While the B and the N dopings produce opposite effects. The HOMO-LUMO gap of the N-doped CCCNTs is the widest among all the gaps of the CCCNTs.