Ti-MWW分子筛吸附H2O和NH3的结构和振动光谱的密度泛函理论计算

Ti-MWW分子筛具有10元环(10MR)孔道体系和12MR超笼以及外表面杯状空穴,在以H2O2水溶液为氧化剂的催化氧化反应中表现出不同于其他钛硅分子筛的特殊溶剂效应和立体选择性.已有的实验和密度泛函理论(DFT)计算研究表明,骨架Ti(IV)可能分布在10MR孔道和12MR超笼中.最近,我们采用DFT计算研究了Ti-MWW分子筛中骨架钛落位,通过比较Ti/Si替代能和红外振动光谱,提出Ti(IV)最可能落位在T1和T3位,并以[Ti(OSi)4]形态存在,显示960 cm–1钛特征振动峰.[Ti(OSi)4]物种水解时Ti–O键发生选择性断裂,生成具有翻转Ti–OH的[Ti(OSi)3OH]物种.由于Ti中心具有Lewis酸性,与配体分子络合后使Ti(IV)的配位状态改变. Ti-MWW分子筛中不同的骨架Ti(IV)落位和形态可能呈现不同的催化选择性.本文应用DFT研究了Ti-MWW分子筛中T1和T3位上不同钛物种与H2O和NH3的吸附作用,考察了其几何结构、吸附能以及红外振动光谱性质,为深入理解骨架Ti(IV)的微观结构及实验红外光谱表征提供参考数据.计算采用36T簇模型,从MWW分子筛晶体结构中分别以T1和T3为中心截取七层骨架原子,末端设为Si–H键并固定为1.46?.结构优化时松弛内部四层骨架原子并固定最外三层骨架原子.所有计算在B3LYP/6-31G(d,p)理论水平完成,计算的吸附能都经过BSSE校正,计算的频率以约化因子0.961校正.所有计算在Gaussian 09软件包完成.计算结果表明,四配位的[Ti(OSi)4]和[Ti(OSi)3OH]物种都能与H2O或NH3分子作用生成三角双锥的五配位络合物. H2O或NH3分子有选择性地进攻Ti–O键的Ti端,形成近乎直线的L–Ti–O键, L–Ti距离可达2.2–2.4?. T1位钛物种的Lewis酸性比T3位的略高.对于[Ti(OSi)3OH]物种, Ti–OH的存在使得Ti(IV)的酸性大大增强,表现出很强的吸附作用.此外,[Ti(OSi)3OH]物种也能通过Ti–OH基团与H2O和NH3形成氢键络合物,但是其吸附能比形成配位络合物的能量更小,说明配体分子更趋向于吸附在Ti中心形成配位络合物.自然键轨道分析表明, Ti(IV)中心的Lewis酸性归因于Ti的空4p轨道接受配体提供的孤对电子,并且属于LUMO+3.所有吸附络合物的特征振动频率分布在两个区域,即钛特征振动区域和羟基振动区域. T1和T3位的[Ti(OSi)4]物种的钛特征振动频率都在960 cm–1,与H2O形成五配位的吸附络合物之后,钛特征振动频率位移到970 cm–1.[Ti(OSi)3OH]物种的钛特征振动频率分别为990 cm–1(T1位)和970 cm–1(T3位),吸附H2O分子后都位移到980 cm–1.相应的NH3吸附络合物的钛特征振动峰频率都高出5 cm–1.分析表明,钛特征振动模式归属于Ti–O–Si键的不对称伸缩振动的协同振动.在羟基伸缩振动区域,气相H2O、末端Si–OH基团以及Ti–OH基团的羟基伸缩振动在3600–3760 cm–1.吸附H2O后,羟基伸缩振动移到3460–3150 cm–1区域.[Ti(OSi)3OH]物种与NH3和H2O形成氢键络合物后,钛羟基的伸缩振动频率分别红移500和1100 cm–1,出现在2700和3200 cm–1区域.吸附分子的O–H和N–H的伸缩振动频率略微蓝移,这反映了Ti物种具有Lewis酸性.     

4-硝基咪唑A-带激发态结构动力学

通过共振拉曼光谱实验和量子化学计算的方法研究了4-硝基咪唑(4NI)A-带激发态衰变动力学. 对4NI的振动光谱、紫外电子吸收光谱、荧光光谱和共振拉曼光谱进行了指认. 在全活化空间自洽场法(CASSCF)/6-31G(d)计算水平下获得了单重激发态S₁(n_Oπ^*)和S₂(ππ^*)和势能面交叉点S₁(n_Oπ^*)/S₂(ππ^*)的优化几何结构和能量, 分析了A-带共振拉曼光谱的强度模式特征, 获得了短时结构动力学, 并结合全活化空间自洽场法(CASSCF)理论计算结果确定了4NI 在S₂(ππ^*)态衰变通道主要是S_{2, FC}→S_{2, min}(ππ^*)→S₀辐射弛豫.     

Influence of Ga/(Ga + In) grading on deep‐defect states of Cu(In,Ga)Se2 solar cells

The benefits of gallium (Ga) grading on Cu(In,Ga)Se₂ (CIGS) solar cell performance are demonstrated by comparing with ungraded CIGS cells. Using drive‐level capacitance profiling (DLCP) and admittance spectroscopy (AS) analyses, we show the influence of Ga grading on the spatial variation of deep defects, free‐carrier densities in the CIGS absorber, and their impact on the cell's open‐circuit voltage V_oc. The parameter most constraining the cell's V_oc is found to be the deep‐defect density close to the space charge region (SCR). In ungraded devices, high deep‐defect concentrations (4.2 × 10¹⁶cm^–3) were observed near the SCR, offering a source for Shockley–Read–Hall recombination, reducing the cell's V_oc. In graded devices, the deep‐defect densities near the SCR decreased by one order of magnitude (2.5 × 10¹⁵ cm^–3) for back surface graded devices, and almost two orders of magnitude (8.6 × 10¹⁴ cm^–3) for double surface graded devices, enhancing the cell's V_oc. In compositionally graded devices, the free‐carrier density in the absorber's bulk decreased in tandem with the ratio of gallium to gallium plus indium ratio GGI = Ga/(Ga + In), increasing the activation energy, hindering the ionization of the defect states at room temperature and enhancing their role as recombination centers within the energy band. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

通过双Σ型激光方案控制振动态布居转移

通过使用含时量子波包方法,对HF分子该类型的布居转移动力学进行了研究. 提出双Σ型激光控制方案,用于控制布居从|v=16>能级向|v=0>能级进行转移. 该方案的第一步是将布居从|v=16>经过中间能级|v=11>向|v=7>转移,第二步是将布居从|v=7>经过中间能级|v=3>向|v=0>转移. 在每一个步骤中,三个振动能级在两束重叠的激光脉冲作用下形成一个Σ型的布居转移路径. 通过优化激光的强度、频率和延迟时间,得到了最大的布居转移效率. 计算并比较了正序脉冲和反序脉冲两种情况,在这两种情况下,布居都可以超过90%从|v=16>能级向|v=0>能级进行转移.     

硅烯中受电场调控的体能隙和朗道能级

近年来, 硅烯(单层硅)由于其独特的结构和电子性质以及在量子霍尔效应等领域的潜在应用而成为理论和实验研究的一个热点. 借助于四带次近邻紧束缚模型, 详细计算和研究了硅烯中受电场调制的体能隙和电子能级. 结果表明: 硅烯原胞中的两个子格处于不同的平面上, 可以通过外电场区分和控制这两个子格, 这将破坏在纯石墨烯中无法被破坏的K-K'对称性, 并消除由这一对称性导致的电子能级的二重简并; 外加电场还会引起硅烯中次近邻格点之间的Rashba自旋轨道耦合, 这一作用会在不同狄拉克点有选择地消除电子能级在部分电场点的简并, 相邻能级从交叉状态变为反交叉状态; 电子能级中除一些孤立的交叉点外, 每个能级都具有确定的自旋取向, 石墨烯中电子能级的四重简并在硅烯中被完全消除, 从而导致填充因子ν=0, ±1, ±2, ±3,…的量子霍尔平台.     

磁场中的拓扑绝缘体边缘态性质

用数值方法研究了拓扑绝缘体薄膜体系在外加垂直磁场 作用下其边缘态的性质. 磁场的加入通过耦合k+eA, 即Peierls势替换关系和 该作用导致的Zeeman交换场体现在哈密顿量中. 考虑窄条圆环状结构的二维InAs/GaSb/AlSb薄膜量子阱材料, 当其处于拓扑非平庸状态, 即量子自旋霍尔态时, 会出现受时间反演对称性保护的两支简并边缘态, 而在垂直磁场的作用下, 时间反演对称性被破坏, 这时能带将形成一条条的朗道能级, 原来简并的两支边缘态也会分开到朗道能级谱线的两侧, 从电子态密度的空间分布情况则可以看到边缘态分别局域在材料的两个边界. 随着磁场的增大, 位于同一边界上的不同 自旋极化的边缘态将出现分离: 一支仍然局域在边缘, 另一支则随外加磁场的增加而有逐渐演化到材料内部的趋势. 文中还计算了同一边界上的两支边缘态之间的散射, 结果表明由于两个边缘态在空间发生分离, 相互之间的散射被很大的压制, 得到了其散射随磁场增加没有明显变化的结论, 所以磁场并不会增强散射过程, 也没有破坏体拓扑材料的性质, 说明了量子自旋霍尔态在没有时间反演对称的情况下也可以有较强的稳定性.     

Glow Discharge Characteristics of Hollow Needle-Plate Electrode in Atmospheric Pressure ArgonSCIEI北大核心CSCD

Atmosphere pressure uniform plasma has the broad application prospect in the industrial field. Using hollow needle cathode - plate anode device excited by direct-current voltage, a uniform and stable glow discharge is generated at atmospheric pressure in ambient air with argon used as working gas. The influence of the experimental parameters (including gas flow rate and the gas gap width) on discharge has been investigated by optical method. It can be found that a glow-discharge plasma column can bridge the two electrodes. The plasma column is uniform, and no filaments can be discerned. Near the plate electrode, the diameter of the plasma column is largest of all positions. The maximal diameter of the plasma column increases with increasing the discharge current or the gas flow rate. Through electrical method, the voltage-current characteristic has been investigated. It has been found that the discharge voltage decreases with increasing the current which is similar with the characteristic of glow discharge in low pressure. It increases with increasing the gas gap width or the gas flow rate. By analyzing the optical emission spectrum scanning from 330 to 450 nm emitted from the direct-current glow discharge, the molecular vibrational temperature and the intensity ratio of spectral lines I-391.4/I-337.1 have been investigated as functions of the gas flow rate and gas gap width. Results indicate that both the vibrational temperature and the intensity ratio of spectral lines I-391.4/I-337.1 decrease with increasing the gas flow rate or the gas gap width. In addition, the molecular vibrational temperature and the intensity ratio of spectral lines I-391.4/I-337.1 have been investigated in spatial resolution along the direction of gas flow(plasma column axial), and give a qualitative analysis as well. It is found that the vibrational temperature and the average electron energy increase with increasing the distance from the hollow needle cathode. These results are important to the industrial applications of glow discharge.     

Fatigue crack growth behavior of Al7050-T7451 attachment lugs under flight spectrum variation

This paper discusses an analytical and experimental investigations of the fatigue crack growth behavior in attachment lugs subjected to a randomized flight-by-flight spectrum. In the analysis, the stress intensity factors for through-the-thickness cracks initiating from lug holes were compared by weight function method, boundary element method (BEM), the interpolation of Brussat’s solution. The stress intensity factors of a corner crack at a transition region were obtained using two parameter weight function method and correction factors. Fatigue life under a load spectrum was predicted using stress intensity factors and Willenborg retardation model considering the effects of a tensile overload. Experiments were performed under a load spectrum and compared with the fatigue life prediction using the stress intensity factors by different methods. Changes of fatigue life and aspect ratio according to the clipping level of the spectrum were discussed through experiment and prediction. Effect of the spectrum clipping level on the fatigue life was experimentally evaluated by using beach marks of fractured surface.     

Nonequilibrium vibration-dissociation phenomena behind a propagating shock wave: Vibrational population calculation

An analysis of nonequilibrium phenomena behind a plane shock is presented concerning the vibrational relaxation and the dissociation of a pure diatomic gas. In the first part, the temperature range is 600 K–2500 K and the dissociation processes are neglected. The population of each vibrational level is computed by solving relaxation and conservation equations. The relaxation process is described by the master equations of each vibrational level. The vibrational transition probabilities appearing in the relaxation equations are calculated analytically and take into account the anharmonicity of molecular vibration and the potential angular dependence. The populations obtained are compared to those calculated using a Treanor model and to those calculated with a nonequilibrium Boltzmann distribution. For moderately high levels significant differences may be observed. The importance of the V-V process is found to be weak for the transitions involving the lowest levels. In the second part, the temperature range is 2500 K–5500K and the dissociation process is taken into account as well as the gas dynamic behavior which did not appear in several recent works. The kinetic equations are transformed to obtain a first order differential system and the resolution of such a system coupled with the conservation equations leads to the population of each vibrational level. The vibrational transition probabilities associated with the atom-molecule interaction are deduced from the cross section calculation used in the first part. The bound-free transition probabilities are obtained, following Marrone and Treanor, assuming that dissociation must occur preferentially from the higher vibrational states: the Marrone and Treanor probability model is extended and employed with an anharmonic oscillator. In the present investigation, behind the shock wave, the evolution of the population distribution expressed as a function of the distance is not monotonous: a lag time appears as shown experimentally in previous works for the macroscopic parameters. For moderately high levels the influence of the anharmonicity and those of the V-V processes appear significant and strongly related. In a general way, in both temperature ranges investigated, the V-V processes reduce the effects of the T-V transfer. Finally the influence of thecharacteristic probability temperature U of Marrone and Treanor is analyzed and a method of determination of local varying U is proposed.     

Shock waves in molecular solids: ultrafast vibrational spectroscopy of the first nanosecond

A novel technique which uses a microfabricated shock target array assembly is described, where the passage of a shock front through a thin (0.5μm) polycrystalline layer and the subsequent unloading process is monitored in real time with ultrafast coherent Raman spectroscopy. Using a high repetition rate laser shock generation technique, high resolution, coherent Raman spectra are obtained in shocked anthracene and in a high explosive material, NTO, with time resolution of ∼ 50 ps. Spectroscopic measurements are presented which yield the shock pressure (up to 5 GPa), the shock velocity (∼ 4 km/s), the shock front risetime (t _r < 25 ps), and the temperature (∼ 400°C). A brief discussion is presented, how this new technique can be used to determine the Hugoniot, the equation of state, the entropy increase across the shock front, and monitor shock induced chemical reactions in real time. Received 28 October 1996 / Accepted 12 November 1996