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.     

引力波探测中的被动隔振系统

介绍了引力波探测实验中的被动隔振系统的基本原理和研究现状,讨论其性能及特点.低频被动隔振系统,如七级气体弹簧隔振系统,多级隔振堆,四级悬臂弹簧隔振系统以及三级弯曲弹簧隔振系统在10Hz以上,都具有好的隔振性能;倒摆、折叠摆、 X摆和锥摆等超低频水平隔振系统实现了几十秒的共振周期;建立在对称扭杆弹簧系统基础上,构思新颖的被动垂直隔振系统克服了传统被动垂直隔振系统无法解决的困难,实现了超低频被动垂直隔振.      

机械系统摩擦动力学研究进展

摩擦环节对机械系统动力学行为有重要、甚至可能是关键的影响. 深入研究摩擦及摩擦动力学特点,对于解决机械系统中摩擦带来的不利影响, 发挥其有利作用, 是非常重要的. 本文介绍和评述了机械系统摩擦动力学的研究进展, 包括常用的摩擦模型及其特性, 摩擦系统自激振动、强迫振动和摩擦振动控制等. 除理论研究方法之外, 重点讨论了制动噪声振动、摩擦耗能和多领域摩擦振动控制等摩擦动力学的应用研究.     

Hitting probabilities and the Hausdorff dimension of the inverse images of a class of anisotropic random fields

Let X = {X(t):t ∈ R~N} be an anisotropic random field with values in R~d.Under certain conditions on X,we establish upper and lower bounds on the hitting probabilities of X in terms of respectively Hausdorff measure and Bessel-Riesz capacity.We also obtain the Hausdorff dimension of its inverse image,and the Hausdorff and packing dimensions of its level sets.These results are applicable to non-linear solutions of stochastic heat equations driven by a white in time and spatially homogeneous Gaussian noise and anisotropic Guassian random fields.     

Accumulation of Particles and Formation of a Dissipative Structure in a Nonequilibrium Bath

The standard textbooks contain good explanations of how and why equilibrium thermodynamics emerges in a reservoir with particles that are subjected to Gaussian noise. However, in systems that convert or transport energy, the noise is often not Gaussian. Instead, displacements exhibit an α-stable distribution. Such noise is commonly called Lévy noise. With such noise, we see a thermodynamics that deviates from what traditional equilibrium theory stipulates. In addition, with particles that can propel themselves, so-called active particles, we find that the rules of equilibrium thermodynamics no longer apply. No general nonequilibrium thermodynamic theory is available and understanding is often ad hoc. We study a system with overdamped particles that are subjected to Lévy noise. We pick a system with a geometry that leads to concise formulae to describe the accumulation of particles in a cavity. The nonhomogeneous distribution of particles can be seen as a dissipative structure, i.e., a lower-entropy steady state that allows for throughput of energy and concurrent production of entropy. After the mechanism that maintains nonequilibrium is switched off, the relaxation back to homogeneity represents an increase in entropy and a decrease of free energy. For our setup we can analytically connect the nonequilibrium noise and active particle behavior to entropy decrease and energy buildup with simple and intuitive formulae.     

Wavelet Bases for Confinements of the Infrared Divergence

We propose the construction of wavelet bases with pseudo-polynomials adapted to the homogeneous Sobolev spaces , s−n/2∈ℕ. They provide a confinement of the infrared divergence by decomposing as a direct sum X ⊕ Y where X is a “small” space which carries the divergence and Y can be embedded in . In the case of we also construct such an orthonormal basis, which provides a confinement of the Mumford process.     

Nonnormality and stochastic differential equations

A highly nonnormal Jacobian may give rise to large transients. This behaviour has been shown to have implications for (a) the relevance of linearising a nonlinear system and (b) the timestep restrictions required to keep a numerical method stable. Here, we show that nonnormality also manifests itself for stochastic differential equations. We give an example of a family of systems that is stable without noise, but can be made exponentially unstable in mean-square by a noise perturbation that shrinks to zero as the nonnormality increases. We then show via finite-time convergence theory that an Euler approximation shares the same property, giving a discrete analogue of the result. In memory of Germund Dahlquist (1925–2005).AMS subject classification (2000) 65C30, 34F05     

天文观测相机低噪声CCD视频处理电路的分析与设计

在讨论天文观测相机低噪声视频处理电路的基础上,对前置放大、差分放大、可编程增益放大、相关双采样及16bit模数转换等关键组成部分进行了分析,给出各组成部分的设计方法。对所设计的低噪声视频处理电路进行了PSPICE仿真和实验测试,仿真和实验结果表明,该视频处理电路在本身引入噪声较小的同时,有效地抑制了CCD的复位噪声和1/f等低频噪声,使天文观测相机的整机噪声<15e-,达到了指标要求。     

草酸钙结石形态的红外光谱分析

草酸钙结石主要是以一水草酸钙(COM)、二水草酸钙(COD)的形式存在。在解决缺少COD标样的难题后,将制备的COD样品与COM标样混合,然后采用红外光谱法对混合物进行分析研究,采用谱带比值法,确定了COD和COM在660和610 cm-1处与780和520 cm-1处的吸收度比值(R)与质量分数(w)的关系式,其线性回归方程分别为:R=11.95×10-3wCOD 0.873 61,r=0.983 63;R=4.74×10-3wCOD 0.886 52,r=0.992 44。同时为了减少压片、测定等因素引起的误差,采用零点交叉一阶导数法,测定在1 320 cm-1处吸收度一阶导数与COD质量分数(w)的关系式,其线性回归方程I=5.5×10-5w 9.2×10-5,r=0.996 60。线性良好。     

红外光谱在定量分析中的应用

本文对近十年红外光谱在定量分析中的应用进行了概述。偏最小二乘法,一阶导数、二阶导数等化学计量法在定量分析中得到了普遍的应用,反射、探针、漫反射等技术的发展拓宽了红外光谱定量分析的领域。固体、液体、气体均可计量的优势更加突出。实现了单一物质,二元或多元物质的定量测定。