Fe3O4表面逆水煤气反应的DFT研究

采用密度泛函理论（DFT）研究了Fe3O4（111）表面逆水煤气反应的机理（氧化还原机理和中间产物分解机理）。通过优化初始构型,得到了最稳定的吸附构型。对两种机理主要的基元反应活化能进行了比较,结果表明：氧化还原机理是主要的反应机理,中间产物分解机理较难发生。计算结果还表明八面体Fe原子在吸附和活化过程中起着重要作用。     

Dynamic density forecasts for multivariate asset returns

We propose a simple and flexible framework for forecasting the joint density of asset returns. The multinormal distribution is augmented with a polynomial in (time‐varying) non‐central co‐moments of assets. We estimate the coefficients of the polynomial via the method of moments for a carefully selected set of co‐moments. In an extensive empirical study, we compare the proposed model with a range of other models widely used in the literature. Employing a recently proposed as well as standard techniques to evaluate multivariate forecasts, we conclude that the augmented joint density provides highly accurate forecasts of the ‘negative tail’ of the joint distribution. Copyright © 2010 John Wiley & Sons, Ltd.     

Atomic layer deposition on Pd nanocrystals for forming Pd-TiO2 interface toward enhanced CO oxidation

Pd typically exhibits relatively low catalytic activity in CO oxidation, as CO is apt to be adsorbed on Pd to poison the surface for O2 activation. In this Letter, we report that this limitation can be overcome by integrating Pd with TiO2. The TiO2 was coated on Pd nanocubes with a controllable thickness using atomic layer deposition (ALD) method. Given the different work functions of TiO2 and Pd, the electrons in TiO2 semiconductor will flow toward Pd. With the electron density increased on Pd, the adsorption of CO to Pd will be weakened while the oxygen activation can be facilitated. Meanwhile, the interface-confined sites at Pd-TiO2 may further enhance the oxygen activation. As the species adsorption and activation are strongly correlated with electron density, the performance of Pd-TiO2 in CO oxidation turns out to depend on the TiO2 thickness, which determines the number of transferred electrons, within a certain range (<1.8 nm). This work provides a new strategy for enhancing catalytic performance through tailoring charge densities in hybrid catalysts.     

Alternative synthetic route for the heterometallic CO-releasing [Sb@Rh12(CO)27]3− icosahedral carbonyl cluster and synthesis of its new unsaturated [Sb@Rh12(CO)24]4− and dimeric [{Sb@Rh12Sb(CO)25}2Rh(CO)2PPh3]7− derivatives

The evolution of the optical absorption spectrum of bimetallic Ag-Au monolayer-protected clusters (MPC) obtained by progressively doping Ag into the experimentally known structure of Au133(SR)52 was predicted via rigorous time-dependent density-functional theory (TDDFT) calculations. In addition to monometallic Au133(SR)52 and Ag133(SR)52 species, 5 different (Ag-Au)133(SR)52 homotops were considered with varying Ag content and site positioning, and their electronic structure and optical response were analyzed in terms of Projected Density Of States (PDOS), the induced or transition electron density, and Transition Component Maps (TCM) at selected excitation energies. It was found that Ag doping led to the effects rather different from those encountered in bare metal clusters. And it was also observed that Ag doping could produce structured spectral features, especially in the 3–4 eV range but also in the optical region if Ag atoms were located in the sub-staple region, as rationalized by the accompanying electronic analysis. Additionally, Au doping into the staples of Ag-rich MPC also gave rise to a more homogeneous induced electron density. These findings show the great sensitivity of the electronic response of MPC nanoalloy systems to the exact location of the alloying sites.     

NaCl和KCl溶液康普顿散射的影响因素

自康普顿散射提出以来,其理论研究和应用研究一直是国内外的热点。基于NaCl和KCl溶液的康普顿散射,通过一定的近似处理,从理论上分析适合这两种溶液的康普顿散射光子数与溶液浓度之间的关系表达式;然后,通过康普顿散射实验验证康普顿散射的理论和实验研究。为了从更微观的角度来把握NaCl和KCl溶液康普顿散射的机理,笔者立足于密度泛函理论对NaCl与KCl溶液的电子结构作了深入分析,得出结论:除质量密度、散射衰减因子以及溶液的浓度外,电子数密度和电子受到的束缚也对康普顿散射光子数有影响,其中,电子数密度是影响NaCl与KCl溶液康普顿散射光子数的主要因素。     

功率谱估计在扫描隧道显微术中的应用

扫描隧道显微镜(简称STM)所采集到的隧道电流信号,不仅包含着表征样品的表面形貌和分子结构的有效信号,而且还隐含着整个扫描隧道显微系统的动态特性.针对STM采集的信号,运用短时傅立叶变换对其波形数据进行功率谱密度估计,对信号在频率域中的特征向量加以提取.结果表明:基于谱空间的特征向量,准确地分辨出了工频在信号中的干扰,也能有效地解释和分析STM系统的动态特性,进而认为存在一小阻尼系统对信号施以影响;此外,分析的结果可以为STM扫描过程的控制,诊断以及扫描图像的重建和解释提供有力的理论指导.     

导体椭圆柱面的电荷及场强的分布

利用复变函数保角变换,将无限长导体椭圆柱面变换为无限长导体圆柱面,给出了无限长导体椭圆柱面电荷密度和空间电场分布.     

基于多维概率分布的多金属矿床储量估算模型

为解决不同边界品位下多金属矿床的储量快速估算问题,针对多金属矿床有用组分之间具有相关性的特点,基于多维概率分布函数建立了多金属矿床储量估算数学模型.以某金铜矿床为例,分析证明了矿床中金、铜品位的概率密度呈对数正态分布,并对金、铜品位分布的相关性特征进行检验.在此基础上将一维概率密度扩展至多维,建立了金铜矿床品位分布的多维概率密度函数,得出了不同边界品位下矿床保有的资源储量,并进行了可靠性验证.结果表明,模型的计算误差在10%以内,符合储量管理的精度要求.     

装药缺陷对熔铸炸药爆速影响的实验研究

为研究装药缺陷对熔铸炸药爆速的影响,采用缺陷分类的研究方法对含有不同缺陷的RDX/TNT熔铸混合炸药进行了爆速实验研究.实验结果表明存在于不同组分中的缺陷会对爆速产生不同程度的影响,TNT中的缺陷使爆速降低幅度最大,若对炸药爆速有较高要求则应重点去除TNT内缺陷,并且推断缺陷尺寸大小可能是影响爆速的决定性因素.对现有ω-Г爆速计算公式进行改进使其能够体现装药缺陷对爆速的影响.     

CdS,ZnO1-xSx电子结构和光学特性的第一性原理研究

 采用基于密度泛函理论(DFT)框架下广义梯度近似(GGA)的PBE平面波超软赝势方法,研究了闪锌矿型CdS和ZnO_1-xS_x(x=0,0.25,0.5,0.75,1)的电子结构和光学特性.计算并分析了闪锌矿型CdS和ZnO_1-xS_x的复介电函数、光电导率、吸收系数和损失函数.研究结果表明,闪锌矿型CdS和ZnO_1-xS_x(x=0,0.25,0.5,0.75,1)均为直接带隙半导体材料.ZnO中一定浓度的硫掺杂,导致带隙宽度变窄,而晶格常数随掺杂基本呈线性变化.就目前制备铜铟镓硒(CIGS)薄膜太阳能电池普遍使用CdS缓冲层而言,ZnO_1-xS_x具有与CdS类似的电子结构,但光学特性上高频特性有明显改善.这些特性对于改善电池吸收层表面性能和光吸收特性、制备高效CIGS薄膜太阳能电池非常有利.